- Email: [email protected]
Theoretical screening and design of SM315-based porphyrin dyes for highly efficient dye-sensitized solar cells with near-IR light harvesting
Accepted Manuscript Theoretical screening and design of SM315-based porphyrin dyes for highly efficient dye-sensitized solar cells with near-IR light harvesting Yan Fu, Tian Lu, Yongxin Xu, Minjie Li, Zhen Wei, Huan Liu, Wencong Lu PII:
S0143-7208(17)32372-0
DOI:
10.1016/j.dyepig.2018.03.045
Reference:
DYPI 6630
To appear in:
Dyes and Pigments
Received Date: 24 November 2017 Revised Date:
17 March 2018
Accepted Date: 22 March 2018
Please cite this article as: Fu Y, Lu T, Xu Y, Li M, Wei Z, Liu H, Lu W, Theoretical screening and design of SM315-based porphyrin dyes for highly efficient dye-sensitized solar cells with near-IR light harvesting, Dyes and Pigments (2018), doi: 10.1016/j.dyepig.2018.03.045. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
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Theoretical Screening and Design of SM315-Based Porphyrin Dyes for Highly
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Efficient Dye-Sensitized Solar Cells with Near-IR Light Harvesting
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Yan Fu, Tian Lu, Yongxin Xu, Minjie Li*, Zhen Wei, Huan Liu, Wencong Lu*
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Email:[email protected]; [email protected]
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Tel:+86-21-66133513
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ACCEPTED MANUSCRIPT Abstract: We screened five π-conjugated bridges and further designed four dyes
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FSQ101-FSQ104 with screened π-linker B1 as bridge, four electron-rich units D1-D4
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as donors and electron-withdrawing cyanoacrylic acid as acceptor, based on
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experimentally synthesized dye SM315 for highly efficient dye-sensitized solar cells
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(DSSCs) using density functional theory (DFT) and time-dependent density
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functional theory (TDDFT) methods. Our theoretical results reveal that designed dyes
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FSQ101-FSQ104 have not only remarkably better light harvesting abilities toward the
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near-infrared (NIR) region with broader light harvesting efficiency (LHE) curves and
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higher maximum short circuit current densities ( J scmax ), but also obviously narrower
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band gaps, larger adsorption energies (Eads), lower exciton binding energies (EBEs),
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larger conduction band energy shifts (∆ECB ) compared to dye SM315. Therefore, the
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designed dyes FSQ101-FSQ104 might have superior performances and could be
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promising sensitizer candidates for highly efficient DSSCs.
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Graphical Abstract
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Keywords: Porphyrin dyes, DFT/TDDFT, D-π-A structure, Vis/NIR, Optoelectronic
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properties
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1. Introduction Dye-sensitized solar cells (DSSCs) have been widely investigated due to low
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manufacturing costs, ease of fabrication, and tunable aesthetic features of color and
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transparency [1-5], since the seminal work was reported by O’Regan and Grätzel with
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the power conversion efficiency (PCE) of 7.1% in 1991 [6]. Generally, such device
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mainly consists of a dye sensitizer, a metal oxide semiconductor (typically TiO2) as a
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photoanode, a redox electrolyte and a counter electrode (cathode) [7]. As one of the
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most crucial components in DSSCs, the sensitizer plays a significant role in light
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capturing and electron injection which impacts on PCE [2]. Over the last two decades,
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ruthenium complexes [8], metal-free organic dyes [9, 10] and porphyrin sensitizers [3,
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11, 12] have been fully investigated.
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Although the PCE of DSSCs based on ruthenium dyes has reached 11% [13] under
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simulated AM 1.5 irradiation (100 mW cm-2), such as dyes N3 and N719 [14], their
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further application might be limited for rarity and environmental concerns [15]. Thus,
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it is still imperative to develop efficient noble-metal-free sensitizers. Among the dyes,
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porphyrin has aroused wide attention due to its structural similarities to chlorophylls
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in natural photosynthetic systems, as well as its exceptional photophysical properties
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and electrochemical stabilities [16, 17].
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Benefitting from its heterocyclic macrocycle with a π-aromatic core, porphyrin
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shows an intense Soret band (B band) at 350-500 nm and a moderately weak Q band
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at 550-700 nm in the visible region [18, 19]. In general, porphyrin-based dyes employ
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the donor-π bridge-acceptor (D-π-A) structure. It has been revealed that the
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photophysical and electrochemical properties of porphyrins and the efficiencies of 4
ACCEPTED MANUSCRIPT DSSCs could be greatly tuned with molecular engineering on π-conjugated bridge,
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electron-donating and electron-accepting moieties [20-27]. In 2011, Yella et al.
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reported a D-π-A type porphyrin dye YD2-o-C8 with cosensitizer Y123 reaching a
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high PCE of 12.3% [3]. Since then, great efforts have been devoted to reengineer the
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structure of YD2-o-C8 for improving the light-harvesting capability. In 2014, Grätzel
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and co-workers synthesized dyes GY50 [21] and SM315 [12] by introducing
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2,1,3-benzothiadiazole (BTD) as a π bridge and simultaneously well-engineered
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donor based on YD2-o-C8, achieving a higher efficiency of 12.75% and a record
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efficiency of 13%, respectively, in a cobalt(II/III)-based ([Co(bpy)3]2+/3+) redox
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electrolyte without co-sensitizers.
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Even though porphyrin sensitizers exhibit a spectral feature covering the visible
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absorption region, 400-700 nm, it is still imperative to engineer the structures of
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D-π-A porphyrin sensitizers with enhanced NIR harvesting to improve the
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photovoltaic performance. However, it would be time-consuming and cost-expensive
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to synthesize porphyrins by conventional experimental approaches [13, 28, 29].
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Fortunately, theoretical calculation with low cost is becoming a powerful tool for the
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design of efficient dyes in DSSCs.
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In this paper, a series of porphyrin derivatives have been studied in theory
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systematically, based on experimentally synthesized dye SM315 with the record PCE
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by introducing better donors, π-bridges, and acceptor for more efficient porphyrin
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dyes. The models of all investigated dyes are shown in Figure 1. The photoelectrical
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properties including the ground-state geometries, frontier molecular orbitals (FMOs), 5
ACCEPTED MANUSCRIPT energy levels and absorption spectra and charge transfer (CT) characters of dyes were
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predicted using the density functional theory (DFT) and time dependent density
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functional theory (TDDFT) methods [30, 31]. In addition, some key parameters
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related to PCE were predicted, including exciton binding energy (EBE), light
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harvesting efficiency (LHE) curve, maximum short circuit current density ( J scmax ),
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injection driving energy (∆Ginj), driving force of regeneration (∆Greg), conduction
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band energy shift (∆ECB) and dipole moment (µnormal). We hope our work could offer
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theoretical guideline for experimentalists in the effective design of highly efficient
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porphyrin sensitizers to improve the PCE of DSSCs.
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Figure 1. Chemical structures of the studied Zn-porphyrin dyes. The hexyl and octyl groups are
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replaced by methyl groups marked with dashed and solid circles, respectively.
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2. Computational Details
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The ground-state geometries of the dye molecules were fully optimized at hybrid
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DFT levels by B3LYP function with LANL2DZ basis set, which has been proven to
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be relatively reliable for optimizing the geometries of porphyrin dyes [16, 32]. On the 6
ACCEPTED MANUSCRIPT basis of ground-state optimized geometries, the vibrational frequency calculations
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were performed at the same level of theory to confirm that the optimized geometries
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are local minima (no imaginary frequencies) on the potential energy surfaces. The 12
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lowest singlet-singlet excitations were calculated using the TD-DFT method in
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conjunction with the linear-response IEF-PCM model (integral equation formalism
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polarizable continuum model) in its non-equilibrium limit [33, 34] in solvent
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tetrahydrofuran (THF) phase without any further parameter.
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With the aim to select a reliable functional to evaluate the vertical excitation
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energies, different time-dependent density functionals, including TD-B3LYP [35],
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TD-CAM-B3LYP [16, 36], TD-PBE0 [32], TD-HSE0 [37, 38], TD-BHandHLYP [39],
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TD-M06 and TD-M062X [40] were used. To enhance the computing efficiency, the
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hexyl and octyl groups of the dyes were replaced by methyl groups, which has been
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proved to have negligible effect on the photovoltaic properties of the porphyrin dyes
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[32, 41]. The absorption spectra by different methods along with experimental values
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of SM315 are presented in Figure S1 and Table S1. The maximum absorption
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wavelengths and band shapes indicate that TD-CAM-B3LYP is the optimal functional
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in general to be implemented to simulate the excited states of subject dye[12].
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Furthermore, the 0-0 energy[78] of SM315 (Table S1) using TD-CAM-B3LYP also
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has been conducted to make sure the reliability of the calculation for optical
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properties[12]. Although we are aware that such comparison between theoretical 0-0
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energy and experimental data should be made with care, the 0-0 energy simulations
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with various TD-DFT methods would be time-consuming and beyond our scope here.
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ACCEPTED MANUSCRIPT Therefore, we choose the CAM-B3LYP functional to predict the optical properties of
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the investigated dyes. Frontier molecular orbital energy levels were obtained at the
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TD-CAM-B3LYP/LANL2DZ/IEF-PCM level in THF. The oxidation potential
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energies were determined at the M06/6-311G(d,p) level in THF [41]. All the
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calculations of the studied dyes were performed with DFT and TDDFT methods using
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the Gaussian 09 package [46]. For the further exploration of intramolecular charge
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transfer (ICT) from donor to acceptor [5, 42], the electron density difference maps
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(EDDs) and two charge transfer parameters (qCT, DCT) [43, 44] from the ground state
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(S0) to the first excited state (S1) were also investigated by Multiwfn 3.4 code [45].
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To gain an insight into the coupling interactions between dyes and TiO2 surface, the
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photoelectrical properties of porphyrin dyes adsorbed on the (TiO2)38 cluster were
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investigated with DFT calculations using DMol3 program [47, 48] in Material Studio
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Version 7.0. The geometries of (TiO2)38 cluster and dye-(TiO2)38 complexes were
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optimized using the generalized gradient-corrected approximation (GGA) method [49]
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with Perdew-Burke-Ernzerhof (PBE) functional [50, 51] and double numerical
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polarization (DNP) basis set. The excitation energy of (TiO2)38 cluster is in good
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agreement with the experimental results of the TiO2 semiconductor, proven to be a
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reasonable model to mimic the effects of the semiconductor surface in previous works
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[52, 53]. All dyes were adsorbed on the TiO2 surface through bidentate bridging mode
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[54], which is one of the stable modes for carboxylic acid anchor on TiO2 surface [55,
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56]. Then, the electronic structures of dye-(TiO2)38 complexes were investigated
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through single point calculations at the CAM-B3LYP/SVP/IEF-PCM level [57] in
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THF using the Gaussian 09 package. Subsequently, the simulated total density of
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states (TDOS) of the (TiO2)38 cluster and partial density of states (PDOS) of TiO2 in
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the dye-(TiO2)38 complexes were obtained with GaussSum 3.0.1 [58].
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3. Results and Discussion
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3.1 Screening of π-Conjugated Bridge
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The π-conjugated bridge is a key part of the D-π-A structure in dye for high
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performance DSSC devices. To screen predominant π-bridge candidate of porphyrin
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derivatives, we simulated molecular geometries, electronic structures and the
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characteristics of absorption spectra of five screened dyes F101-F105 (Figure 1) by
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introducing different π-conjugated bridges B1-B5 based on experimentally synthesized
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dye SM315.
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The optimized structures and geometrical parameters of the investigated dyes are
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illustrated in Figure S2 and Table S2, respectively. The dihedral angles Φ1 between
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π-linkers and acceptors in the screened dyes and SM315 are all close to 0°. The
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dihedral angles Φ2 formed between BTD and π-linkers in dyes F101-F105 are
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predicted to be -0.08°, -0.76°, 0.01°, 0.01°and -0.02°, respectively, which also
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approximate to 0°. However, the dihedral angle Φ2 of SM315 is -25.63° for the steric
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repulsion between hydrogen atoms. Therefore, the introducing of π-linkers B1-B5
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effectively improves the coplanarity of the screened dyes, which might be beneficial
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to intramolecular charge transfer behaviors [59].
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To investigate the effect of π-linkers on the electronic properties, the electron
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density distributions of frontier molecular orbitals (FMOs, Figure 2) for the studied 9
ACCEPTED MANUSCRIPT dyes were performed. The electron density of HOMO for the screened dyes and
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SM315 is mainly localized on the donor group to the porphyrin ring moiety and partly
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spreaded over BTD moiety, while the electron density of LUMO plentifully
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distributes on the acceptor group, π-bridge and BTD moiety, less electron density
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around the porphyrin core. Such distinct charge separated states would facilitate the
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efficient electron injection from dyes to the conduction band of semiconductor (TiO2),
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while the overlap on the porphyrin macrocycle and BTD moiety of FMOs is
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beneficial for ICT transition [60] in the absorption process.
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Figure 2. Frontier molecular orbitals of the studied dyes at the TD-CAM-B3LYP/ LANL2DZ/
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IEF-PCM level in THF as solvent.
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The energy levels and HOMO-LUMO band gaps of the investigated dyes were also
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performed (Figure 3). Clearly, the LUMO energy levels of all dyes are above the
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conduction band of TiO2 (-4.00 eV) and the HOMO energy levels are sufficiently
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lower than the oxidation potential of [Co(bpy)3]2+/3+ electrolyte (-5.00 eV) [61, 62],
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indicating all dyes could inject electrons from the excited sensitizers into the 10
ACCEPTED MANUSCRIPT conduction band of TiO2 and quickly recapture the injected electrons by the reduced
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species in the electrolyte. The HOMO-LUMO band gaps of F101-F105 are smaller
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than that of SM315 (3.55 eV). The results confirm that the LUMO energy levels can
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be decreased via different π-bridges and thence band gaps could be tuned.
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Figure 3. Frontier molecular orbital energy levels obtained at the TD-CAM-B3LYP/ LANL2DZ/
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IEF- PCM level in THF as solvent.
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To unveil the effect of the π-linkers on the absorption and light harvesting abilities,
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the UV-visible absorption spectra (Figure 4, Table 1) and charge transfer properties
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(Table 2) of the dyes were carried out. Apparently, the absorption spectra of the
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screened dyes show obviously red-shifted Q bands and similar Soret bands compared
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to SM315. The molar extinction coefficients corresponding to λmax of dyes
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F101-F105 are 6.6108 × 104, 6.4199 × 104, 5.0607 × 104, 6.1287 × 104, 5.6652 × 104
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M-1 cm-1, respectively, exhibiting an increment of 22.4%-59.9%, compared to SM315
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(4.1342 × 104 M-1 cm-1). From Table 1, the maximum absorption wavelength (λmax)
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of F101 has 52 nm redshift compared to SM315.
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Charge transfer process plays an important role in DSSCs. The electron density
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difference maps (EDDs) and charge transfer parameters (transferred charge qCT and
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spatial distance DCT) [43] [44] for the dyes are shown in Table 2. With the 11
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the donor, while the increasing electron density (purple) primarily distributes on the
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acceptor as well as BTD. The results show that the screened dyes perform
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comparable abilities in intramolecular charge transfer from donor to acceptor versus
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SM315. Furthermore, the values of qCT and DCT for the screened dyes are larger than
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the figures for SM315 (Table 2). Among the screened dyes and SM315, F101 has the
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best charge transfer performance with 0.658 e for qCT and 4.853 Å for DCT.
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Above all, we believe that π-bridge B1 will be the excellent π-conjugated bridge
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candidate for high-efficiency dyes in DSSCs and thence B1 was selected for the
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further design.
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Figure 4. The stimulated UV-Visible absorption spectra of the investigated dyes in THF solution.
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3.2 Design of D−π−A Structure
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Four dyes FSQ101-FSQ104 (Figure 1) were designed by employing the screened
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B1 as π-bridge, four strong electron-donating moieties D1-D4 as donor groups, and 12
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acid) as anchoring group based on dye SM315. The optimized structures and
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geometrical parameters of dyes FSQ101-104 are shown in Figure S2 and Table S2.
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The dihedral angles Φ1 and Φ2 in the designed dyes are all close to 0°, which would
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facilitate the intramolecular electron transfer. [63, 64]. From the Figure 2, it’s obvious
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that the electron density of HOMO for the designed dyes is mainly localized on the
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donor group as well as π-bridge and the density of LUMO is centered on the accepter,
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which could benefit the electron injection from dyes to semiconductor. Conspicuously,
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the energy levels of the designed dyes (Figure 3) could match the conduction band of
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TiO2 (-4.00 eV) and the oxidation potential of [Co(bpy)3]2+/3+ electrolyte. And these
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dyes show remarkably narrower HOMO-LUMO band gaps, especially FSQ101 and
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FSQ102 with the minimal energy gaps 2.92, 2.97 eV, respectively.
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Figure 4 displays the absorption spectra of the designed dyes, where the Q bands
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are significantly broadened and redshifted and the Soret bands are slightly red shifted
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comparing with SM315. And the absorption spectra of the designed dyes are extended
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into NIR region. The λmax of these four dyes are predicted to be 773, 764, 756, 757 nm,
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sequentially, which all achieve great enhancements compared to SM315 (651 nm).
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The molar extinction coefficients corresponding to λmax of dyes FSQ101-FSQ104 are
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9.9435 × 104, 9.7580 × 104, 10.0741 × 104 and 9.7780 × 104 M-1 cm-1, respectively,
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showing a remarkable increment of 136.0%-143.7%, compared to SM315 (4.1342 ×
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104 M-1 cm-1). The EDDs and the values of qCT, DCT also evince that the designed
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dyes gain greater charge transfer characteristics than the screened dyes and SM315.
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Particularly, FSQ101 owns the best performance with 0.719 e for qCT and 6.269 Å for
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DCT. Obviously, the designed dyes with larger λmax, higher molar extinction coefficients,
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higher oscillator strengths, significantly broader and red-shifted absorption spectra
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toward NIR region, larger qCT (e) and DCT (Å) might be promising candidates of
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porphyrin sensitizers in highly efficient DSSCs.
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Table 1. Calculated electronic transition data in termed of excitation energies (E/eV), band
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wavelengths (λ/nm), oscillator Strengths (f), and electronic compositions for the dyes in THF using TD-CAM-B3LYP/LANL2DZ on the IEF-PCM model.a E(eV) 1.76(S0→S1) 3.16(S0→S9)
λ(nm) 703 393
f 1.5806 1.1076
F102
1.80(S0→S1)
688
1.5197
3.16(S0→S8)
F104
1.82(S0→S1)
392
0.9155
679
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F103
F105
FSQ101
FSQ102
H→L(65%) H-2→L+3(38%) H-2→L+1(8%) H →L(67%) H-2→L+2(5%) H-2→L+2(50%) H-1→L+1(5%) H→L(66%) H-2→L+2(6%) H-1→L+2(45%) H→L+1(8%) H→L(67%) H-2→L+2(5%) H-2→L+2(36%) H-1→L+1(8%) H→ L(67%) H-2→L+2(6%) H-2→L+2(38%) H-1→L+1(9%) H→L(60%) H-3→L(5%) H-2→L+3(19%) H-3→L(13%) H→ L(57%)
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Dyes F101
3.19(S0→S8)
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1.1700
1.81(S0→S1)
685
1.4463
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396
1.7063
1.81(S0→S1)
684
1.3446
3.16(S0→S7)
392
1.2668
1.60(S0→S1)
773
2.4426
2.81(S0→S7)
441
1.0833
1.62(S0→S1)
764
2.3902
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Composition H→L+1(11%) H→L+3(9%) H→L+2(8%) H →L+1(10%)
H-1→L(10%) H-2→L+2(9%) H-1→L(6%) H-1→L(10%)
H→L+1(22%)
H-1→L+1(6%)
H→L+1(12%)
H-1→L(9%)
H-4→L(12%)
H-1→L+1(11%)
H→L+1(11%)
H-1→L(9%)
H→L+3(15%) H-1→L+3(6%) H→L+1(11%)
H-3→L+3(12%) H→L+1(5%) H-1→L(9%)
H-2→L+1(11%) H→L+2(5%) H→L+1(13%)
H→L+1(9%) H-4→L(5%) H-1→L(11%)
H→L+1(17%) H-1→L+2(12%) H→L+1 (13%)
H-1→L(17%) H-1→L+1(6%) H-1→L(12%)
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1.0409
FSQ104
1.64(S0→S1) 3.13(S0→S10) 1.64(S0→S1)
756 396 757
2.4606 0.9169 2.3918
SM315
3.07(S0→S8) 1.91(S0→S1)
404 651
1.1799 0.9497
3.14(S0→S6)
394
1.5582
FSQ103
a
H→L+1(15%) H→L+3(31%) H→L+1(13%)
H-1→L(9%) H-2→L+1(26%) H-1→L(10%)
H-1→L(32%) H→L+1(16%)
H→L+2(11%) H-2→L+2(9%)
H→L+1(32%)
H-4→L(11%)
Only orbital percentage >5% are reported; where H=HOMO and L=LUMO.
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H→L+2(11%)
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H-1→L(31%)
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H-3→L(6%) H-2→L+3(41%) H-3→L(5%) H→ L(57%) H-2→L+2(35%) H→ L(58%) H-3→L(7%) H-2→L+3(42%) H→L(63%) H-1→L(7%) H-2→L+2(37%) H-1→L(6%)
Table 2. The EDDs and CT parameters for all dyes corresponding to the S0→S1 transition. qCT (e)
DCT(Å)
F101
0.658
4.853
F102
0.604
3.932
F103
0.637
EDDsa
qCT (e)
DCT(Å)
0.719
6.269
FSQ102
0.693
5.937
4.541
FSQ103
0.658
5.425
0.607
4.171
FSQ104
0.683
5.739
0.634
4.489
SM315
0.564
3.734
Dyes
FSQ101
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F105
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a
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The isosurface of electron density is 0.0002 a.u.
EDDsa
The blue and purple colors symbolizes an decrease and increase in electron density, respectively.
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3.3 Dye Adsorption on the (TiO2)38 cluster In order to simulate the performance of the DSSCs more vividly, we explored the
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photoelectrical properties of porphyrin dye adsorbed on the (TiO2)38 cluster. Evidently,
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the dyes take the bidentate chemisorption with two Ti-O bonds of 2.115-2.152 Å
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(Table 3 and Figure S3) [65-67]. The electron density of HOMO is entirely
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delocalized on the dyes while the density of LUMO is centered on the conductor
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(Figure S4 and Figure 5). It indicates that the studied dyes have sufficient potentials to
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efficiently inject electron into the conduction band of TiO2.
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To figure out the feasibility of electronic injection from dyes to TiO2 surface, the
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adsorption energy (Eads) was estimated from the formula Eads=Edye+TiO2 -Edye-ETiO2,
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where Edye, ETiO2, and Edye+TiO2 are the total energy of isolated dye, (TiO2)38 cluster,
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and dye-(TiO2)38 complex, respectively [68]. The negative Eads indicates that the
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molecule adsorption is exothermic and stable. The adsorption energies (Table 3) of
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dyes F101-F105 and FSQ101-FSQ104 were predicted to be -16.4, -0.8, -16.2, -16.8,
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-15.9, -17.2, -18.2, -21.5 and -17.1 kcal mol-1, respectively. The adsorption energies of
16
the screened and designed dyes except F102 are comparable or even larger than that
17
of SM315 (15.1 kcal mol-1), which performs stronger interactions between the dyes
18
and the TiO2 surface. The adsorption energy of F102 is only -0.8 kcal mol-1, due to a
19
larger geometric distortion between dye and TiO2 surface. The results indicate that the
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designed dyes could potentially lead to faster electron transfer rates and good
21
photovoltaic performances [35, 69].
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Figure 5. HOMO and LUMO orbital isosurfaces of dyes FSQ101-FSQ104 and SM315 adsorbed
3
on (TiO2)38 nanoparticle at the level of CAM-B3LYP/SVP/IEF-PCM.
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Table 3. The bond length (Å), and adsorption energy (kcal mol-1) of dye-(TiO2)38 complexes
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calculated by PBE/DNP in the DMol3 module.
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Dyes
Ti-O(Å)
Ti-O(Å)
Eads(kcal mol-1)
Dyes
Ti-O(Å)
Ti-O(Å)
Eads(kcal mol-1)
F101 F102 F103 F104 F105
2.152 2.143 2.141 2.137 2.144
2.130 2.125 2.125 2.119 2.126
-16.4 -0.8 -16.2 -16.8 -15.9
FSQ101 FSQ102 FSQ103 FSQ104 SM315
2.139 2.146 2.130 2.139 2.149
2.121 2.118 2.115 2.124 2.124
-17.2 -18.2 -21.5 -17.1 -15.1
7 8 9
3.4 The efficiency of DSSCs As known to all, the overall efficiency (η) of DSSCs is determined by the 17
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short-circuit current density (Jsc), the open-circuit voltage (Voc), the fill factor (FF),
2
and the incident solar power (Pinc) under AM 1.5 irradiation (100 mW cm-2). And it
3
can be expressed as [2]
5
η = FF
J scVoc Pinc
(1)
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3.4.1 Short-circuit current density (Jsc)
According to eq(1), enhancing Jsc and Voc are essential to improve the η of DSSCs.
7
Correspondingly, Jsc is the photocurrent per unit area (mA cm-2) when the DSSC
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under irradiation is short-circuited. It is related to the interaction between TiO2
9
semiconductor and dye as well as the absorption coefficient of the dye. The Jsc can be
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described by the following equation [70]
J sc = e ∫ IPCE(λ )I s (λ )d λ = e ∫ LHE(λ )Φ injηregηcoll I s (λ )d λ
(2)
where e is the elementary charge, IPCE(λ) is the incident photon-to-current
13
conversion efficiency at a fixed wavelength and Is(λ) is the corresponding photon flux
14
based on the AM 1.5G (global) solar radiation spectrum. And IPCE(λ) is the product
15
of the light-harvesting efficiency at a relevant wavelength LHE(λ), the electron
16
injection efficiency (Фinj), the regeneration efficiency (ηreg) and the charge collection
17
efficiency (ηcoll).
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According to the experimental investigation performed by Kim et al., the dye with
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a lower exciton binding energy (EBE) will have a higher maximum incident
20
photon-to-current conversion efficiency (IPCE) [71, 72]. The EBE can be viewed as
21
the difference between the electronic and optical band gap energies. And it is
22
evaluated as [73] 18
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EBE=ELUMO－EHOMO－E0-0
(3)
where the E0-0 is an electronic vertical transition energy corresponding to the
3
maximum absorption wavelength. From Table 4, the EBEs of designed dyes are lower
4
than the ones of screened dyes and SM315, which indicates that the designed dyes
5
could be more potential to lead to higher short circuit current densities in DSSCs.
8
harvesting efficiency LHE(λ) can be obtained as followed: [8]
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For the same DSSCs, ηcoll can be seen as a constant. Correspondingly, the light
LHE( λ ) =1−10−Γσ (λ)
(4)
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where Γ is the surface loading of sensitizers (mol cm-2) grafted onto semiconductor
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and σ is the absorption cross section in units of cm2 mol-1 obtained from the decadic
11
extinction coefficient (units of M-1cm-1) by multiplication with 1000 cm3 L-1. Here, Γ
12
is set to 8.35 × 10-7 mol cm-2, according to the experimental value of SM315 [12]. The
13
calculated LHE curves are plotted in Figure 6. The curves are further extended step by
14
step in the order: SM315 < F103< F105 < F104 < F102 < F101 < FSQ103 ≈ FSQ104
15
< FSQ102 < FSQ101. Compared to SM315, the curves of dyes FSQ101-FSQ104 are
16
significantly red-shifted and broadened. Hence the designed dyes are expected to have
17
higher light-harvesting abilities and match better with the solar radiation spectrum.
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Figure 6. The plot of the simulated LHE curves of the studied dyes.
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When Фinj, ηreg and ηcoll are assumed to be unity, the calculated value of Jsc would
5
be the theoretically maximum short circuit current density ( J scmax ), which could be
6
used to reflect the overall light harvesting abilities of the dyes [41]. As is shown in
7
Table 4, it is clear that the J scmax of the designed dyes are higher than those of the
8
screened dyes and SM315, implying that the designed dyes have better light
9
harvesting abilities than other dyes. The calculated J scmax of SM315 (35.69 mA cm-2)
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is higher than the experimental one, because Фinj, ηreg and ηcoll are assumed to be 1.
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According to eq(2), we know that the Фinj and ηreg, which are closely related to the
12
driving force of electron injection (∆Ginj) and regeneration (∆Greg), could influence
13
Jsc . Generally, the ∆Ginj and ∆Greg can be described by [74, 75]
14
∆Ginj = E dye* − ECB = E dye + E0−0 − ECB
(5)
15
∆Greg = Eredox − Edye
(6)
16
where Edye*is the oxidation potential energy of the excited dye, Edye is the ground state 20
ACCEPTED MANUSCRIPT oxidation potential energy of the dye, ECB is the conduction band energy of TiO2
2
(-4.00 eV) and Eredox is the oxidation potential of [Co(bpy)3]2+/3+ (-5.00 eV) [61, 62].
3
The ∆Ginj of all dyes (Table 3) are in the range of 0.31 eV-0.58 eV. Islam et al. have
4
demonstrated that when ∆Ginj is above 0.2 eV, Фinj will be close to the unit [76]. This
5
means that an efficient electron injection occurs from all the investigated dyes into the
6
conduction band of TiO2. Moreover, the ∆Greg of all dyes are in the similar rank of
7
0.22-0.33 eV, indicating an efficient regeneration for all dyes. In a word, the driving
8
forces of electron injection and regeneration of the designed and screened dyes are
9
comparable to those of SM315.
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3.4.2 Open circuit photovoltage Voc
15
Besides the Jsc, the overall power conversion efficiency is also influenced by the open circuit voltage (Voc), which could be expressed as [77]
Voc =
ECB + ∆ECB kbT nc Eredox + ln − q q q N CB
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(7)
where ECB is the conduction band energy of the semiconductor, ∆ECB is the shift of
17
the conduction band energy level, q is the unit charge, kbT is the thermal energy, nc is
18
the number of electrons in the conduction band, NCB is the accessible density of
19
conduction band state.
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The Voc of the dye-(TiO2)38 complex is largely affected by the conduction band
21
energy shift, which is defined as the difference of the energy-axis intercept of the line
22
that fit the low energy contour of the partial density of states (PDOS) of TiO2 in the 21
ACCEPTED MANUSCRIPT complex and that of the total density of states (TDOS) of the TiO2 cluster alone
2
(Figure 7 and Figure S5). All the simulated values are listed in Table 4. The calculated
3
∆ECB of dyes are in the narrow range of 0.145 eV to 0.157 eV. The screened and
4
designed dyes own higher values of ∆ECB than SM315. Especially, the conduction
5
band energy shifts of FSQ101-TiO2 and FSQ104-TiO2 complexes are quite larger than
6
those of other dye-(TiO2)38 complexes.
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Figure 7. Total and partial density of states (DOS) of TiO2 cluster (black) and FSQ101-TiO2
9
complex (red). The intercepts of the dashed lines with the energy axis correspond to the calculated
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CB edges.
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Table 4. Calculated electronic properties of the isolated dyes and dye-(TiO2)38 complexes. Dyes F101 F102 F103 F104
J scmax -2
(mA cm ) 45.03 44.11 42.00 43.71
EBE (eV)
Edye (eV)
Edye* (eV)
Ginject (eV)
Greg (eV)
∆ECB (eV)
1.51 1.59 1.56 1.58
-5.32 -5.29 -5.33 -5.31
-3.56 -3.49 -3.51 -3.50
0.44 0.51 0.49 0.50
0.32 0.29 0.33 0.31
0.148 0.151 0.147 0.149
22
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1.56 1.32 1.35 1.40 1.38 1.64
-5.32 -5.23 -5.22 -5.33 -5.28 -5.33
-3.51 -3.63 -3.60 -3.69 -3.64 -3.42
0.49 0.37 0.40 0.31 0.36 0.58
0.148 0.153 0.145 0.150 0.157 0.147
Data in parenthesis is the experimental value from Ref [12].
2 3
0.32 0.23 0.22 0.33 0.28 0.33
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43.27 52.14 52.01 51.95 51.96 35.69(18.1)a
4. Conclusions
We first screened five dyes F101-F105 with different π-conjugated bridges B1-B5
5
based on experimentally excellent dye SM315. The results indicate that π-linker B1 is
6
the
7
FSQ101-FSQ104 with B1 as π-bridge, four strong electron-donating moieties D1-D4
8
as donor groups and cyanoacrylic acid as anchoring group. Four designed dyes
9
FSQ101-FSQ104 exhibit obviously smaller energy gaps, higher molar extinction
10
coefficients, dramatically broader and red-shifted UV-visible absorption spectra
11
covering the entire visible range up to NIR region. Importantly, the designed dyes also
12
show lower EBEs, larger ∆ECB, remarkably better light-harvesting abilities with
13
broader LHE curves and larger J scmax compared to dye SM315, which could facilitate
14
the improvements of Jsc and Voc and then benefit the increments of the overall power
15
conversion efficiencies in DSSCs. In particular, FSQ101 is the most promising
16
sensitizer candidate for the highly efficient DSSCs. It is expected that this theoretical
17
study will provide valuable strategies for the development of highly efficient D-π-A
18
type porphyrins in future DSSCs.
promising
π-conjugated
bridge.
Then
we
designed
four
dyes
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Corresponding Author *E-mail: [email protected]; [email protected]
Notes The authors declare no competing financial interest.
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Acknowledgements
This study was supported by the National Key Research and Development Program
7
of China (2016YFB0700504), Natural Science Foundation of Shanghai, China
8
(16ZR1411500), Shanghai Municipal Education Commission (Peak Discipline
9
Construction Program) and the High Performance Computing Center of Shanghai
10
University.
11
Appendix A. Supplementary data
Supplementary data related to this article can be found at
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Supporting Information Theoretical Screening and Design of SM315-Based Porphyrin Dyes for Highly Efficient Dye-Sensitized Solar Cells with Near-IR Light Harvesting
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Yan Fu, Yongxin Xu, Tian Lu, Minjie Li*, Zhen Wei, Huan Liu, Wencong Lu*
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Department of Chemistry, College of Science, Shanghai University, Shanghai 200444,
Email:[email protected]; [email protected]
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Tel:+86-21-66133513
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Index
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Table S1…………………………………………………………………………………………. S1 Figure S1………………………………………………………………………………………… S2 Figure S2…………………………………………………………………………………………S3 Table S2.………………………………………………………………………………………….S5 Figure S3.…………………………………………………………………………………………S6 Figure S4.…………………………………………………………………………………………S7 Figure S5.…………………………………………………………………………………………S9 The Cartesian Coordinates of molecules discussed in the text……………………………...…...S10 The Cartesian Coordinates of dyes ……………………………………………………………...S10 F101.……………………………………………………………………………………………..S10 F102.……………………………………………………………………………………………..S14 F103.……………………………………………………………………………………………..S19 F104.……………………………………………………………………………………………..S23 F105.……………………………………………………………………………………………..S27 FSQ101.………………………………………………………………………………………….S31 FSQ102.………………………………………………………………………………………….S35 FSQ103.………………………………………………………………………………………….S39 FSQ104.………………………………………………………………………………………….S44 SM315.…………………………………………………………………………………………...S48 The Cartesian Coordinates of dye-TiO2 complexes……………………………………………...S52 F101-TiO2.……………………………………………………………………………………….S52 F102-TiO2.……………………………………………………………………………………….S59 F103-TiO2.……………………………………………………………………………………….S66 F104-TiO2.……………………………………………………………………………………….S73 F105-TiO2.……………………………………………………………………………………….S80 FSQ101-TiO2.……………………………………………………………………………...…….S87 FSQ102-TiO2.……………………………………………………………………………...…….S93 FSQ103-TiO2.……………………………………………………………………………...…...S100 FSQ104-TiO2.……………………………………………………………………………...…...S107 SM315-TiO2.……………………………………………………………………………...…….S114 The Cartesian Coordinates of TiO2 cluster……………………………………………………..S121
ACCEPTED MANUSCRIPT Table S1. The absorption maxima together with the oscillator strengths (f) and 0-0 energy of dye SM315 in THF solution, calculated at the IEF-PCM-TDDFT /LANL2DZ levels using the optimized geometries. The experimental data are al
λmax(nm) 915 651 819 1001 644 816 639 668a
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f 0.4966 0.9497 0.6739 0.3327 1.0736 0.7349 1.0197 ----
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Functional B3LYP CAM-B3LYP PBE0 HSE06 BHandHLYP M06 M062X Experiment
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so given for comparison.
a
E0-0(eV) ---1.75b ---------------1.79a
The data from reference [12] in manuscript. To reduce the cost of time and computation, only the E0-0 of SM315 using TD-CAM-B3LYP was calculated.
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(a) The band shapes of SM315 with different computational methods
(b) The screenshot of experimental spectra from the original article of SM315 Figure S1 The theoretical and experimental absorption spectra of SM315.
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F101
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FSQ104
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Figure S2. The optimized geometries for the studied dyes at the B3LYP/LANL2DZ
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level.
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Φ1(°) Φ2(°) 0.01 -0.08 -0.44 -0.76 -0.01 0.01 0.02 0.01 -0.02 -0.02 0.00 -0.04 -0.03 0.53 -0.03 -0.67 0.03 -0.10 -0.31 -25.63
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angles. (Φ1, Φ2 represent the dihedral angles)
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Figure S3. The optimized structure of dye-(TiO2)38 adsorption complexes calculated at
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the GGA/PBE/DNP level in DMol3 Program.
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Figure S4. Interacting orbital isosurfaces of dyes F101-F105 adsorbed on (TiO2)38
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nanoparticle.
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Figure S5. Total and partial density of states (DOS) of TiO2 cluster (black) and
dye-TiO2 complex (red). The inercepts of the dashed lines with the energy axis
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correspond to the calculated CB edges.
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The Cartesian Coordinates of molecules discussed in the text The Cartesian Coordinates of dyes
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-4.68222500 -4.11099100 -3.96557300 -2.74742200 -4.86300400 -2.57776800 -4.56855500 -1.20251600 -2.62197100 -3.94577800 -5.93974500 -2.29260200 -3.53832900 -5.62990900 0.34056400 0.17161300 -1.40580700 -4.14218900 -0.99985500 -3.61038400 0.21035200 1.69714500 1.55057700 -0.12033200 -1.49976500 -0.91712600 1.53795500 2.45603600 2.27874800 2.15531300 1.12669200 -1.59497100 -1.50288600 -0.84985000 -0.90241800 1.73403800 3.53559900 3.69731900 3.21848600 1.19841400
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-6.11833100 -5.34752500 -4.41707000 -2.05370300 4.07337200 1.71161800 5.79596800 5.04671500 -5.75992200 -7.16216600 -6.71766300 -4.16411800 -1.62218200 5.42337000 3.80943200 1.26476100 6.84522400 6.42852800 -6.53707800 -7.34014600 -7.16263700 -6.64240000 -2.03894100 -1.90407400 -0.53453000 6.19500300 1.62930300 0.17475800 1.58988700 6.93767700 6.98386800 6.36623100 -0.35569700 -0.28792000 0.66182400 -1.09578000 0.75160900 1.50796800 -1.00634900 -1.81957500 -0.11520300 1.67612500 2.45878400 -1.67924200
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0.07544000 -0.99342200 1.21654900 -1.72944400 -1.37344600 1.86441200 1.74666900 -2.79895200 -1.47017700 -2.43778600 -0.83715700 3.00390000 1.47031300 2.87682100 1.27908800 -3.17751700 -3.36073000 -2.71090400 3.54139000 3.46183800 3.25756800 -4.27643900 4.78447100 -5.21713300 -4.43651800 5.81623500 5.00591700 -6.24395300 -5.07316700 -5.45802900 -3.71970700 7.01141900 5.69151500 6.18934700 3.97913700 -6.36551100 -6.96624000 -6.07781600 -5.52110900 7.19110400 7.77077600 6.36844900 4.09491900 -7.42387100
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-3.28916000 -2.97144600 -1.67059000 -1.90009900 -1.72388600 -1.99723500 -3.43043800 -3.51405700 -3.36361800 -3.31364200 -2.99140900 -1.61859200 -1.58806600 -1.77578400 -1.68131800 -1.94992800 -3.56291000 -2.56488400 -4.34264200 -3.30789300 -2.16986800 -3.95161800 -2.85795000 -1.49476300 -2.58673900 -1.85055000 -0.80406700 -0.98934400 -2.77451300 -2.05869800 3.60201600 5.01439100 5.71155400 5.82371700 7.18992000 5.08175600 7.24457000 5.34659900 7.98045900 7.69277600 6.32810500 7.78123100 -7.40808100 -8.13845500
EP
AC C
C O C O C O C H C H C C H C H C H H H H H H H H H H H H H H C C C C C N C H C N S H N C
S15
ACCEPTED MANUSCRIPT
RI PT
-0.46666900 1.86266100 0.41993800 -1.62883400 0.10469600 2.51194900 2.16855800 1.08191900 -0.40121900 -2.18998800 -2.09604500 -0.47350900 1.00713300 2.14934400 3.30298600 0.75839700 -1.63277900 -3.09945300 -0.01549900 2.90800300 -2.23063100 2.29983700 4.30120500 -2.75430300 -2.32527300 3.05717300 0.91613900 5.08242700 4.79954000 -3.35054300 -2.67058300 -2.91433300 -1.82221200 4.44674400 2.60719000 0.22349200 6.15233200 -3.42707000 -3.72714900 -2.99680000 -2.00652800 5.09463100 0.37899700 0.54938900
SC
1.32088500 -1.56116100 -1.19573800 1.91624100 1.90398200 -2.58888800 -1.32257000 -2.21840900 -0.67271600 3.05437800 1.48240300 3.03235100 1.47906600 -2.94085900 -3.14014000 -2.47274300 3.64320000 3.47016700 3.45344600 -3.99579800 4.88175700 -4.93450800 -4.11531400 5.87284200 5.13723700 -5.92179400 -4.83058700 -5.09639200 -3.39847100 7.05962000 5.72256100 6.31326500 4.15013700 -6.00385800 -6.64250600 -5.83896500 -5.12957300 7.27343100 7.78691300 6.51738500 4.29544500 -7.02526600 -6.84385300 -5.82051500
EP
TE D
M AN U
-8.04095800 -7.53745900 -9.45501700 -7.49910500 -9.19811500 -8.23557500 -6.52351100 -10.14623900 -9.93555500 -8.09439800 -6.62038700 -9.79367400 -9.62713100 -9.55815900 -7.73246800 -11.14895200 -9.25531800 -7.66673900 -10.68138000 -10.28809800 -9.82818700 -11.17762400 -10.10761100 -8.97309900 -11.23105900 -11.82685200 -11.34977400 -10.74662200 -9.46042200 -9.43924200 -7.90004300 -11.72039800 -12.08401400 -11.61135400 -12.49961000 -12.13887500 -10.57143700 -10.82619900 -8.72815000 -12.78156600 -13.52087100 -12.31381000 -11.72283400 -13.18822900
AC C
C C C C C C H C H C H C H C H H C H H C C C C C C C O C H C H C O C H C H C H H C O H H
S16
ACCEPTED MANUSCRIPT
RI PT
-0.83382700 -3.98567800 -1.47075600 -3.07184400 -1.58475200 6.53225900 -4.54023100 7.07013400 6.80985600 6.78783100 -4.91688600 -3.76871200 -5.36551500 -0.49112100 0.24051000 -1.53104100 0.02406700 0.90800100 -0.89292200 0.62102900 -1.16912800 -0.48744200 0.13447700 2.47763000 -2.24782600 -0.81815800 0.96888800 -1.08510500 3.16466000 3.20968200 -1.73796200 -0.41215700 0.59774400 1.91491700 -1.45782300 -1.74803300 4.53710700 2.63200000 4.58317300 2.71050200 -2.25069300 -0.61737500 1.25175500 -2.39702500
SC
-5.57289600 8.40445800 5.17391400 4.37128200 3.38706300 -7.17719400 9.44308700 -6.27951700 -8.02777800 -7.38920000 10.20874500 9.87565600 9.05510100 -0.59287300 0.21731700 -1.77308500 -0.04618000 0.97527200 -1.08076700 0.60440400 -1.41683000 -0.66110500 2.38849400 0.35257200 -2.65897000 -1.06526400 3.46402800 2.69264000 1.02538800 -0.54697600 -2.10978100 -0.63002500 4.79794600 3.26444400 4.02643000 1.88930000 0.80777400 1.72676700 -0.76544000 -1.07714600 -2.71698500 5.08249400 5.60854600 4.23827000
EP
TE D
M AN U
-12.07729500 -11.43045600 -13.90664700 -13.77857900 -13.95612000 -12.14252800 -10.57465100 -12.47814800 -12.76851400 -11.09489900 -11.25607600 -9.92234900 -9.96130600 9.43336300 10.30510400 10.38347600 11.68722800 9.91562300 11.90776900 13.37239400 13.28539100 14.25783000 13.76221300 13.62256500 13.98742300 15.57862800 13.36683600 14.41529400 14.66352600 12.80895300 15.64160000 16.48553200 13.61556600 12.86652300 14.66882600 14.72957100 14.88424200 15.30324400 13.02600000 12.00052400 16.85932600 14.26840100 13.30246800 15.17461300
AC C
H O H H H C C H H H H H H C C S C H C Si C C C C S C C C C C C H C H C H C H C H C C H H
S17
ACCEPTED MANUSCRIPT -0.08901800 1.33383800 -1.45811000 -2.38787600 -3.74870600 6.11338400 -0.25784600 -4.13791600
5.25006300 5.04547200 5.12765500 -1.94923900 -3.15427400 -0.90498000 6.31126600 -3.48014800
RI PT
14.06538600 15.68904100 12.38838200 18.02532600 16.59930300 14.46275700 14.23448600 17.44134700
AC C
EP
TE D
M AN U
SC
C H H O O H H H
S18
ACCEPTED MANUSCRIPT F103
RI PT
0.00143000 -0.92127600 0.88088000 -1.09526400 -1.85004100 0.95606100 1.86365800 -0.12294100 -2.10560300 -2.57406600 -1.92684500 1.95595700 2.52090900 2.02008700 0.86746300 -1.22125200 -2.61659700 -3.35504600 2.37729800 3.31675200 1.86393300 0.67387900 -1.12913800 -2.19777600 -3.69515900 3.46450100 2.29468700 1.56418200 -0.25317200 -2.06680200 -2.72337800 -3.37004300 -5.06163000 4.82534700 3.15477100 3.05396100 1.61531000 -0.29393000 -2.19609300 -3.48911300 -4.37442800 -2.00616300
SC
0.01992500 -0.88789900 0.86342500 -1.11526200 -1.71593200 0.96129600 1.75008000 -0.14440100 -2.06539500 -2.44395300 -1.74001400 1.88653600 2.38257000 1.87138300 0.80777000 -1.23381600 -2.58021400 -3.16409400 2.28222400 3.10980900 1.78257200 0.61141700 -1.16108600 -2.19315600 -3.62285200 3.31676400 2.19909500 1.48100600 -0.30426200 -2.09600100 -2.73032700 -4.99582600 -3.26025400 2.93899000 4.69621200 2.94226400 1.52704900 -0.35493600 -2.23936700 -3.48935600 -5.98470600 -5.28141200
TE D
M AN U
-3.16874700 -2.59861100 -2.45149500 -1.23532700 -3.35153800 -1.06362700 -3.05416100 0.31043200 -1.11066500 -2.43508100 -4.42834400 -0.77776000 -2.02357000 -4.11561800 1.85410400 1.68325300 0.10475500 -2.63219600 0.51498100 -2.09527100 1.72499900 3.21085100 3.06266200 1.39072600 0.01032000 0.59868300 3.05304700 3.97047900 3.79131400 3.66651800 2.63737700 -0.08413100 0.00674300 0.66382100 0.61623100 3.24986600 5.05012600 5.21092400 4.72957200 2.70858800 -0.18017700 -0.07305700
EP
AC C
C C C N C N C Zn C C H C C H N N C H C H C C C C C C C C C C C C C C C H H C H H C O
S19
ACCEPTED MANUSCRIPT
RI PT
-6.08088900 -5.31026100 5.85369300 5.05899200 4.16842400 1.79547400 -5.72087000 -4.11998000 -1.56997000 -7.12763600 -6.68810000 5.50876000 6.89598800 6.42822000 3.92592300 1.37755800 -6.49978700 -1.93361800 -1.90397200 -0.47956200 -7.24380500 -7.20353600 -6.61643100 6.29468700 7.03050300 6.34426400 6.90199600 1.68294500 1.78234800 0.28811500 -0.28410300 -0.21420500 0.71661800 -1.00176100 0.80802200 1.54201400 -0.91016500 -1.71108900 -0.03845800 1.71445100 2.47542200 -1.56605300 0.04931900 0.64440900
SC
-4.23393000 -1.89146100 3.90404300 1.56468700 5.67682400 4.99725400 -5.58768900 -7.03631900 -6.66517000 -3.95075300 -1.42042900 5.26473200 3.60909700 1.07712200 6.73363100 6.39192700 -6.34290200 -7.27472500 -7.10357000 -6.62171200 -1.82164800 -1.68726200 -0.33439700 6.01355400 1.42375400 -0.01088200 1.38834800 6.89053500 6.93718800 6.36205300 -0.35335600 -0.29312700 0.61940700 -1.07344000 0.70106300 1.43567200 -0.99128700 -1.76928800 -0.13677200 1.59068400 2.34764900 -1.64031700 0.09352800 -0.98555100
TE D
M AN U
-0.08772100 0.09962000 0.74649100 0.63800700 0.69823400 0.54927000 -0.18028500 -0.25252000 -0.19736300 -0.09081200 0.10407200 0.76261800 0.79621200 0.72587900 0.71220400 0.56221600 -0.25368300 0.64144200 -1.14778300 -0.17531200 0.96283200 -0.82888100 0.18736600 0.82593300 -0.12529300 0.69851400 1.66704100 1.49248700 -0.30156500 0.50117500 6.44201300 7.85081600 8.49650400 8.70397100 9.97096600 7.81948100 10.12103800 8.26624000 10.80677500 10.42337300 9.01368800 10.69626900 -4.61381200 -5.33968400
EP
AC C
C O C O C O C H C H C C H C H C H H H H H H H H H H H H H H C C C C C N C H C N S H N C
S20
ACCEPTED MANUSCRIPT
RI PT
-0.49750800 1.68717300 0.18660100 -1.60401100 0.06208400 2.25174900 2.04837200 0.76431600 -0.62494100 -2.12247100 -2.06193900 -0.47366000 0.92271500 1.81656100 3.03335900 0.38633000 -1.57587500 -2.99108300 -0.02592500 2.48985100 -2.12192100 1.79972500 3.88151700 -2.55527300 -2.25157900 2.48008900 0.41705700 4.58620400 4.44110200 -3.09670200 -2.44198700 -2.78789000 -1.83723000 3.87152600 1.96826300 -0.35733000 5.65931100 -3.21051600 -3.40396000 -2.89639800 -2.05836000 4.43867100 -0.23398600 -0.07601200
SC
1.24883700 -1.74522000 -1.35261300 1.92168800 1.76923300 -2.82421200 -1.49641300 -2.42707600 -0.79826300 3.07504300 1.53622100 2.91382500 1.28277800 -3.18992900 -3.40347200 -2.68989000 3.60296700 3.55222900 3.28655800 -4.30004600 4.86088400 -5.22597100 -4.48640200 5.90045300 5.08983500 -6.26397900 -5.05583900 -5.51965700 -3.78133100 7.10998000 5.76979400 6.28749300 4.05597500 -6.41180400 -6.97543400 -6.04482500 -5.60301300 7.29653900 7.87451200 6.47231100 4.18186400 -7.47909900 -7.04712400 -6.06506700
EP
TE D
M AN U
-5.25702800 -4.76157200 -6.62879300 -4.69040600 -6.44917900 -5.45606800 -3.76848400 -7.31695800 -7.09021800 -5.29523400 -3.78468300 -7.05336800 -6.89828900 -6.75279300 -4.97007300 -8.29817900 -6.49004800 -4.84728200 -7.96749800 -7.48472600 -7.07266100 -8.32655300 -7.35653900 -6.22464500 -8.47735600 -8.98185500 -8.44569300 -8.00204900 -6.74762800 -6.69898100 -5.15175900 -8.97483400 -9.32243400 -8.81980200 -9.61928800 -9.18161100 -7.86819800 -8.08736100 -5.99360300 -10.03718800 -10.75596400 -9.52360800 -8.74892500 -10.24374600
AC C
C C C C C C H C H C H C H C H H C H H C C C C C C C O C H C H C O C H C H C H H C O H H
S21
ACCEPTED MANUSCRIPT
RI PT
-1.39668800 -3.72327100 -1.48531100 -3.12513000 -1.70355000 5.87279900 -4.18177300 6.44036600 6.08260800 6.15960600 -4.53960100 -3.36090700 -5.00331400 0.01976500 -1.05824900 0.82752400 -0.34057600 0.62395200 1.53796600 1.16205700 -0.74843900 -0.29002900 -1.74224500 -1.99445000
SC
-5.72476800 8.44484400 5.01948500 4.31401200 3.24163200 -7.69978500 9.53468800 -6.83607200 -8.57383900 -7.90633600 10.30508900 9.93560400 9.21089600 -0.08708500 -1.15306300 0.70362900 -0.45439700 0.49619100 1.40499700 1.02173400 -0.86236200 -0.41640000 -1.84022800 -2.09290100
M AN U
-9.08255500 -8.69935200 -11.17731700 -10.98290000 -11.18324400 -9.40624300 -7.85028300 -9.77993000 -10.02623700 -8.36565000 -8.53644900 -7.23934300 -7.19606300 12.26179700 13.27017100 13.07911500 14.76878800 14.47409300 12.66345800 15.25484900 16.10680300 17.17778500 16.08490500 17.00113500
AC C
EP
TE D
H O H H H C C H H H H H H C S C C C H H C O O H
S22
ACCEPTED MANUSCRIPT F104
EP
TE D
M AN U
SC
RI PT
-4.26224900 -0.01030700 -0.01894400 -3.65708000 -0.91483000 -0.92230900 -3.57829300 0.85851100 0.86231300 -2.28650400 -1.11362800 -1.07163300 -4.37625200 -1.76967700 -1.85365600 -2.19440100 0.98751500 0.95929900 -4.21651500 1.74321800 1.82431000 -0.77871300 -0.09900700 -0.08462300 -2.12424200 -2.07210300 -2.06888800 -3.43223800 -2.48500200 -2.55448000 -5.45091300 -1.81834400 -1.94721100 -1.94541200 1.93039500 1.95277200 -3.21113700 2.40554500 2.49102500 -5.28286500 1.84338200 1.96111800 0.72707800 0.89783100 0.91999500 0.63574100 -1.17028100 -1.14723800 -0.88972300 -2.56580300 -2.55343800 -3.60062200 -3.21803700 -3.33020400 -0.66908400 2.35924700 2.39036400 -3.31201100 3.14055400 3.27653000 0.56018700 1.88070600 1.90249300 2.09111000 0.72892700 0.75116600 2.01179200 -1.06661500 -1.03268800 0.38057700 -2.14627200 -2.11737800 -0.94295700 -3.62168300 -3.62181500 -0.62617200 3.40702700 3.46714700 1.87129800 2.33131700 2.35017900 2.81636900 1.62522000 1.64348400 2.70692300 -0.18452400 -0.15485100 2.65119100 -1.99862200 -1.94931100 1.64710600 -2.66218200 -2.61588600 -1.01249000 -4.99294000 -3.28358700 -0.93131700 -3.27363400 -4.99204600 -0.57784000 3.04522300 4.83304000 -0.63184600 4.78317200 3.14277300 2.03912000 3.08741700 3.10365600 3.89374900 1.69565800 1.71169300 4.12820900 -0.20496600 -0.17064800 3.71913300 -2.12041700 -2.05911000 1.74748400 -3.42788700 -3.37168000 -1.06921300 -5.99420400 -4.27869300 -1.01862300 -5.26404800 -1.91669000
AC C
C C C N C N C Zn C C H C C H N N C H C H C C C C C C C C C C C C C C C H H C H H C O
S23
ACCEPTED MANUSCRIPT
RI PT
-6.00221800 -5.25400400 5.85213200 5.08133100 4.14694700 1.77926400 -5.62918300 -4.01408400 -1.46776600 -7.05190500 -6.63659800 5.49267000 6.89835800 6.45729200 3.89313200 1.34641500 -6.40097700 -1.80965400 -1.81386800 -0.37767200 -7.17346300 -7.16464800 -6.57544900 6.27134300 7.03894300 6.38494600 6.94595700 1.66281100 1.72967400 0.25644500 -0.13872500 -0.04340800 0.88537900 -0.80307000 1.00267200 1.68632300 -0.68745000 -1.50985400 0.18430900 1.90324200 2.62760700 -1.32284400 0.00571100 0.60315200
SC
-4.25976000 -1.90579400 4.02260900 1.67325400 5.77601000 5.06841000 -5.61141300 -7.04445900 -6.64559600 -3.98774200 -1.44939600 5.37960600 3.73990600 1.20236400 6.83025800 6.45848400 -6.37620700 -7.23970500 -7.10911500 -6.59019000 -1.83640900 -1.74331400 -0.36102200 6.13789100 1.53804100 0.11318600 1.53775800 6.98130000 6.98834700 6.41570700 -0.17600200 -0.08259100 0.85757800 -0.85446300 0.97387200 1.67070700 -0.73998700 -1.57014100 0.14273800 1.88604700 2.62287500 -1.38530400 0.03063900 -1.05722000
TE D
M AN U
-0.98663200 -0.86473200 -0.53414100 -0.57902100 -0.58909900 -0.68026700 -1.05518000 -1.12252400 -1.11955400 -0.97827100 -0.84778200 -0.54041100 -0.49705200 -0.50838700 -0.59298700 -0.69097400 -1.09850000 -0.26073400 -2.05358500 -1.11828100 0.02930800 -1.76542100 -0.79080900 -0.50718100 -1.37811300 -0.51210300 0.41674200 0.22218900 -1.57395100 -0.73158700 5.35848300 6.76442100 7.37176800 7.65009500 8.84225100 6.66208600 9.06284600 7.24090300 9.71349000 9.25852000 7.81898300 9.66459900 -5.70938700 -6.41973900
EP
AC C
C O C O C O C H C H C C H C H C H H H H H H H H H H H H H H C C C C C N C H C N S H N C
S24
ACCEPTED MANUSCRIPT
RI PT
-0.56523500 1.65996600 0.13427000 -1.67361700 -0.02786200 2.22700000 2.02994900 0.71470400 -0.68819400 -2.21564000 -2.11445700 -0.58687800 0.83388300 1.78075900 3.01947200 0.32783500 -1.69152300 -3.08502400 -0.15570000 2.45623100 -2.26251000 1.76605600 3.85054200 -2.70041100 -2.41244800 2.44879700 0.38096400 4.55761600 4.41011500 -3.26492400 -2.57213800 -2.97181600 -1.99363500 3.84277900 1.93685000 -0.39165100 5.63255600 -3.39814400 -3.57449100 -3.09571800 -2.23285100 4.41215300 -0.25726900 -0.11868500
SC
1.16433000 -1.79483300 -1.45573000 1.83422700 1.66672200 -2.88258500 -1.52246400 -2.53861500 -0.91944400 2.96706500 1.46235100 2.79068300 1.18253500 -3.27954300 -3.44419300 -2.82527300 3.47657400 3.44195600 3.14983400 -4.39860300 4.71400400 -5.34686000 -4.57130800 5.76518300 4.91131700 -6.39231200 -5.19042600 -5.61177000 -3.84965600 6.95659200 5.65901500 6.09052400 3.86576700 -6.52587800 -7.12025400 -6.19926800 -5.68390500 7.11212300 7.73136800 6.25128100 3.95889300 -7.60262700 -7.19210000 -6.23793200
EP
TE D
M AN U
-6.36990000 -5.83838500 -7.69553300 -5.80347700 -7.57985200 -6.51691700 -4.85479300 -8.36807100 -8.15892600 -6.42616700 -4.88370200 -8.20143300 -8.02929200 -7.80068000 -6.02778900 -9.33909200 -7.63893500 -5.97726400 -9.12886200 -8.51685000 -8.24117900 -9.33348600 -8.39826300 -7.40997100 -9.64866400 -9.97434700 -9.44325500 -9.02942300 -7.80910700 -7.90288500 -6.33607100 -10.16453600 -10.47702100 -9.82238400 -10.59274700 -10.15360000 -8.90393700 -9.29335600 -7.20980000 -11.22912300 -11.91011100 -10.50992500 -9.70273600 -11.21741200
AC C
C C C C C C H C H C H C H C H H C H H C C C C C C C O C H C H C O C H C H C H H C O H H
S25
ACCEPTED MANUSCRIPT
RI PT
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SC
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EP
TE D
M AN U
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AC C
H O H H H C C H H H H H H C S C C C H C H C S C H C H C O O H
S26
ACCEPTED MANUSCRIPT F105
RI PT
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SC
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EP
TE D
M AN U
-3.85997500 -3.32333800 -3.11161600 -1.96783500 -4.10811400 -1.72108100 -3.67991600 -0.38727600 -1.87902900 -3.21853000 -5.18638400 -1.40012400 -2.62610800 -4.73590900 1.19136300 0.94527600 -0.68274200 -3.44314100 -0.09291200 -2.66985700 1.09826600 2.54055400 2.32722700 0.61754300 -0.81587200 0.02946300 2.44134500 3.33200200 3.08727300 2.89672600 1.84435800 -0.92967100 -0.83790900 0.11415900 0.06492400 2.66558700 4.41304300 4.50470400 3.95447400 1.88763400 -1.06260000 -0.89850700
AC C
C C C N C N C Zn C C H C C H N N C H C H C C C C C C C C C C C C C C C H H C H H C O
S27
ACCEPTED MANUSCRIPT
RI PT
-6.12588900 -5.35741400 5.79690900 5.00527100 4.11244500 1.74301000 -5.76519700 -4.16419600 -1.61534000 -7.17219200 -6.73474300 5.45140300 6.83812300 6.37269500 3.86942200 1.32454200 -6.54315900 -1.99486000 -1.93187300 -0.52550200 -7.30782900 -7.23155500 -6.66402400 6.23576900 6.99184000 6.28981900 6.82723200 1.61139000 1.74613300 0.23652000 -0.44692200 -0.40334400 0.51351300 -1.20536400 0.57666100 1.35055100 -1.14107000 -1.90502700 -0.28362800 1.47214300 2.25917600 -1.80667800 0.09356300 0.69850800
SC
-4.25926200 -1.92147500 3.85204600 1.51495900 5.62548800 4.94881500 -5.61145200 -7.06011600 -6.69247300 -3.97496900 -1.44915200 5.21227100 3.55621500 1.02604400 6.68190400 6.34307900 -6.36434700 -7.31852900 -7.11119900 -6.65053300 -1.86571900 -1.69802800 -0.36493600 5.95981700 1.38766500 -0.06132100 1.32075000 6.82486000 6.90369500 6.31441100 -0.50496100 -0.47167100 0.42940700 -1.26959500 0.48229100 1.26034600 -1.21552100 -1.95780500 -0.37282900 1.36375300 2.15004200 -1.87682800 0.13860200 -0.93041100
TE D
M AN U
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EP
AC C
C O C O C O C H C H C C H C H C H H H H H H H H H H H H H H C C C C C N C H C N S H N C
S28
ACCEPTED MANUSCRIPT
RI PT
-0.44090800 1.73246900 0.25869600 -1.55292400 0.13606100 2.30588600 2.07974200 0.84501200 -0.54577400 -2.05988000 -2.02415000 -0.38843500 1.00117100 1.88839100 3.08025500 0.48074600 -1.49607000 -2.93293400 0.07238400 2.57043200 -2.03099700 1.89032000 3.96025900 -2.47125000 -2.14330600 2.57821900 0.50933400 4.67240900 4.51244600 -3.00336100 -2.37121200 -2.67013000 -1.72219100 3.96747100 2.07398700 -0.25653900 5.74372700 -3.10020700 -3.31667800 -2.76561200 -1.92724100 4.54274100 -0.13831300 0.03716700
SC
1.30468600 -1.69878400 -1.27911200 1.97304600 1.84006900 -2.76882200 -1.46371900 -2.34478200 -0.71758800 3.13637200 1.57638600 2.99456300 1.35736800 -3.11644800 -3.35542800 -2.59383300 3.67911600 3.61001400 3.37856700 -4.21759400 4.94641000 -5.13241800 -4.40643500 5.97622200 5.19387100 -6.16269900 -4.95979900 -5.43199000 -3.70946500 7.19350300 5.83120700 6.39951600 4.16957100 -6.31341000 -6.86592300 -5.93954700 -5.51773800 7.39831000 7.94987600 6.59835000 4.31391800 -7.37231200 -6.94705000 -5.94697700
EP
TE D
M AN U
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AC C
C C C C C C H C H C H C H C H H C H H C C C C C C C O C H C H C O C H C H C H H C O H H
S29
ACCEPTED MANUSCRIPT
RI PT
-1.29694700 -3.60233700 -1.34736400 -2.99111000 -1.57032600 5.97503100 -4.06773100 6.54826100 6.19189400 6.24818400 -4.41535700 -3.25297700 -4.89778100 -0.25053300 0.53962900 -1.36782500 1.25431400 0.29216200 -0.68634200 0.98172500 -0.92636700 -0.12329200 -1.63845100 -0.08226500 0.65317300 -0.98675200 -0.92815300
SC
-5.62045900 8.55602400 5.15504900 4.45190800 3.37805800 -7.59607200 9.63613800 -6.72858800 -8.46279800 -7.81556600 10.41638600 10.02670500 9.30631000 -0.34913900 0.42699400 -1.45972500 1.13610800 0.17400200 -0.79514300 0.84682100 -1.04072500 -0.25142200 -1.74737100 -0.21937400 0.50421000 -1.11744600 -1.06508800
TE D
M AN U
-9.86079800 -9.32158900 -11.81801900 -11.65022800 -11.84840000 -10.11946800 -8.46386200 -10.47534100 -10.74727200 -9.07785200 -9.14411900 -7.83821300 -7.82353900 11.56149200 12.40406800 12.52316600 12.00877100 13.78106400 14.04940400 15.29632200 15.42497500 16.23886200 15.83225500 17.69327000 18.39389300 18.26620000 19.24679000
AC C
EP
H O H H H C C H H H H H H C C S H C C S C C H C O O H
S30
ACCEPTED MANUSCRIPT FSQ101
RI PT
0.08390600 0.06636700 0.08915400 0.05299400 0.06003800 0.07967200 0.10551900 0.05520900 0.03850100 0.04265600 0.06795900 0.08993100 0.10589200 0.11509100 0.05742500 0.03090900 0.02274800 0.03386500 0.08605500 0.11600600 0.07125200 0.04621200 0.02314100 0.01960700 0.00922100 0.09899400 0.06828800 0.05300400 0.03023500 0.00659100 0.00435800 -1.21012200 1.21557700 -1.10755200 1.31808600 0.07688600 0.04694500 0.02095300 -0.00188400 -0.00636200 -1.23330900 -2.35817400
SC
0.10637500 1.38580700 -1.14084000 1.61702900 2.65361900 -1.30636000 -2.44146500 0.18996500 2.99997700 3.64847400 2.75989200 -2.67850100 -3.38912200 -2.59926300 -1.23606200 1.68804200 3.68059300 4.71713700 -3.29881300 -4.46422900 -2.62592500 -1.00916500 1.52494800 3.06724500 5.18318600 -4.80158700 -3.27056300 -2.27867200 0.27429500 2.82679900 3.77482500 5.89834400 5.92030500 -5.53831700 -5.51718000 -4.33908000 -2.38468300 0.28868000 2.98269300 4.84980900 7.31031500 5.10816300
EP
TE D
M AN U
-5.83628100 -5.20786100 -5.14734300 -3.83750400 -5.91451500 -3.76704900 -5.79165500 -2.33800200 -3.66195200 -4.96149900 -6.98936900 -3.52489200 -4.79157700 -6.86018400 -0.84014500 -0.91000000 -2.42024300 -5.12009000 -2.25102600 -4.89802200 -1.01777900 0.52397200 0.46330300 -1.15534800 -2.46072200 -2.21870000 0.28820800 1.24052700 1.15068200 1.11310000 0.11613600 -2.48663700 -2.47657600 -2.20707600 -2.19602000 0.44831100 2.31707800 2.56797900 2.18218900 0.22485600 -2.52708900 -2.46904900
AC C
C C C N C N C Zn C C H C C H N N C H C H C C C C C C C C C C C C C C C H H C H H C O
S31
ACCEPTED MANUSCRIPT
RI PT
1.21362200 2.37757400 -1.10609800 -2.26929600 1.34084400 2.46629200 -0.01598900 -2.17084700 -3.66345200 2.14135300 3.67103800 0.12329300 -2.03402600 -3.56286600 2.27822200 3.77128200 -0.02573100 -3.80831900 -3.79712600 -4.38502900 3.79729300 3.80086100 4.40729400 0.13267300 -3.69488100 -4.29892100 -3.68732300 3.89814500 3.92262900 4.49300800 0.01381000 0.00692800 0.01626700 -0.00867700 0.00980000 0.03109800 -0.01493800 -0.01617000 -0.00628900 0.01986500 0.03761700 -0.02714800 0.09784100 0.11176600
SC
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TE D
M AN U
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EP
AC C
C O C O C O C H C H C C H C H C H H H H H H H H H H H H H H C C C C C N C H C N S H C C
S32
ACCEPTED MANUSCRIPT
RI PT
0.12886000 0.13208300 0.16000900 0.14430600 0.13147200 0.17527500 0.18086200 0.15168800 0.17549000 0.24263400 0.19943200 0.38091000 -1.05736700 1.10951600 0.15632200 -0.75454600 1.37139900 -1.85668000 -1.61521200 -0.79344400 0.87979000 -0.63857400 -1.09326800 -0.38285300 -2.40788500 -2.58314200 0.82737800 1.48901200 -0.67380900 -1.25937400 0.06231900 1.39716200 -1.29933400 0.03712000 0.73507800 -0.96102300 0.32519400 -0.01281900 -0.03431900 -0.00499200 -0.03121900 -0.01526600 0.00766200 -0.04059900
SC
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EP
TE D
M AN U
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AC C
C C C C H C H C H C N C C H C C H C H H C C H H H H C H C H C H H C H H H C S C C C H C
S33
ACCEPTED MANUSCRIPT -0.01358100 -0.03066900 -0.06098000 -1.13092200 1.12144200 -0.03871700 -0.05538200 -0.03305700 -0.06649700 -0.08309100 -0.06112700 -0.09126300 -0.09262600 -0.08444800 -0.10782700 -0.10033700 -0.11288800
RI PT
-2.15467400 -1.10812100 1.47487700 -3.04197600 -3.01804700 -1.09185600 0.21020600 -1.97413000 0.50108700 1.70475500 -0.37777800 1.64154900 2.98364100 0.59501200 2.89712200 4.03657400 2.82369200
SC
13.01737300 14.11686800 14.71207600 13.09243900 13.10493800 15.51704700 16.05846100 16.14768300 17.44989900 18.13196200 18.09754500 19.61057600 17.49252500 20.28881600 20.19381200 16.95012600 21.17474700
AC C
EP
TE D
M AN U
C C S F F C C H C C H C C O O N H
S34
ACCEPTED MANUSCRIPT FSQ102
SC
RI PT
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EP
TE D
M AN U
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AC C
N C C C C H C H C H H C C C C H C H C H H C C C C C H C H O O O O C H H C H H C H H
S35
ACCEPTED MANUSCRIPT
RI PT
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SC
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TE D
M AN U
11.30857600 10.73575000 10.66259300 12.16137200 8.32983200 7.39218600 6.16582700 4.73986700 4.07833200 4.08872100 2.70285200 4.75050400 2.71439700 4.77661600 1.24566700 2.48899000 3.77062300 5.82248000 2.51432600 3.80392600 5.85143900 -0.21033400 -0.22376400 1.22886900 3.89934300 1.25953700 3.94105000 0.00672800 -1.58072000 -1.59209000 -0.01822900 1.22523600 1.26929400 -1.28028800 -2.26069500 -2.24305500 -2.27881600 -1.30930500 1.23022800 1.21681100 1.27522300 1.27052500 -1.41009300 -3.33379300
EP
AC C
C H H H H C C C C C N C N C Zn C C H C C H N N C H C H C C C C C C C C C C C C C C C H H
S36
ACCEPTED MANUSCRIPT
RI PT
-0.34045700 -0.55368400 0.37836800 1.74695300 -2.05493900 -2.96390300 1.89208600 2.79790400 -0.54095500 -1.91200700 -0.91035300 1.24782600 2.96967600 -3.04051700 -4.32478900 0.74850400 2.87829800 4.15944800 -1.40962600 -3.13365400 -1.02405100 3.04111700 3.03378800 3.78028800 -4.51485500 -4.52945400 -4.96505900 0.86358300 4.36316300 4.79850700 4.35210500 -3.19138400 -3.20996500 -3.94512100 4.79859900 -4.22785700 -0.05571500 -0.03943800 -0.01039600 0.13748200 -0.11631600 0.17243800 0.25078000 -0.08315000
SC
3.04430900 4.95460500 7.61743400 5.55773800 7.36140400 5.06154000 -6.57010000 -4.26894100 -6.82921500 -4.77106500 8.17425200 8.26532000 6.34880100 7.81330900 5.58004500 -7.38438400 -7.02068100 -4.78554600 -7.47817100 -5.56351000 9.25566200 6.97403600 6.98060500 5.61786500 6.17761500 6.18363200 4.69605200 -8.46566600 -5.38467500 -3.90068200 -5.38692100 -6.19253700 -6.19156100 -4.83354000 4.49839900 -5.72269700 0.35551400 0.26810100 0.08159800 -1.25573600 1.12580400 -1.47698800 -2.36205100 0.90847200
TE D
M AN U
-3.35189900 -1.44880200 1.22617700 1.23890700 1.21264200 1.21276700 1.28156800 1.27390000 1.27696300 1.26434800 1.21727500 1.22920100 1.24107400 1.20535200 1.20006500 1.28214200 1.28453000 1.26645600 1.27646200 1.25238900 1.21351800 0.34043300 2.13772900 1.24698300 0.29786500 2.09509600 1.19776900 1.28575300 2.16473900 1.26140000 0.36736400 0.35342100 2.15076300 1.24358500 16.56433500 15.87768100 -3.66055900 -4.88986500 -6.28542700 -6.83989500 -7.21568200 -8.30102200 -6.08583700 -8.61678400
EP
AC C
H H C O C O C O C O C H C H C C H C H C H H H H H H H H H H H H H H H H C C C C C C N C
S37
ACCEPTED MANUSCRIPT
RI PT
-0.22785600 0.05707200 0.31458000 0.40747300 -0.17255200 0.08585000 -0.07994400 0.22784800 0.05490600 0.20945600 0.33704100 0.05260300 0.31902800 0.20695500 -0.08930900 1.54144200 -0.69533700 0.21855900 0.07158300 0.32784200 0.05103000 -0.08292200 0.15985400 -0.06079000 -0.23859800 0.06784700 -0.20101200 -0.36694700 -0.18229400
SC
2.14082900 -0.35276600 -2.76606900 -3.73736600 1.78572100 -0.53514500 0.92540500 -1.71583200 -0.15751300 -1.49163600 -2.67476900 -0.06008400 -2.34950600 -1.33999500 1.20830500 -3.08754500 -3.35352700 -1.36153200 -0.08345600 -2.25440000 0.16788200 1.34462000 -0.72202100 1.24294700 2.63136200 0.18602300 2.47430100 3.69107500 2.37627800
TE D
M AN U
-6.84676000 -9.21764200 -8.66633700 -7.18750900 -9.25334700 -10.65422300 -11.77220100 -11.39690700 -13.17277700 -12.78810600 -10.90795900 -14.60803400 -14.03829600 -15.16652100 -15.83369400 -14.08759900 -14.10235100 -16.56671800 -17.14414000 -17.17247500 -18.54330000 -19.25833000 -19.16623100 -20.73483600 -18.65446800 -21.38405900 -21.35180500 -18.14121800 -22.33042800
AC C
EP
H C N S H C S C C C H C C C S F F C C H C C H C C O O N H
S38
ACCEPTED MANUSCRIPT FSQ103
RI PT
0.10955600 0.13245700 0.15831500 1.21925300 -0.87845800 1.41718200 2.26298700 -1.02957000 -1.94420200 0.21735200 2.56416100 3.09317900 2.33587700 -2.16756900 -2.73954900 -2.05362900 -0.98023400 1.46400300 3.13202000 3.97380900 -2.69410600 -3.62318300 -2.14015600 -0.79777100 1.32254300 2.61722600 4.38772100 -3.94889300 -2.68745900 -1.86368600 0.27279900 2.40953300 3.20584700 5.66013300 4.33016500 -3.88935400 -5.22220200 -3.58206800 -1.95905800 0.27666700 2.53661300 4.10471800
SC
0.02045800 0.02817000 0.04126800 0.75274000 -0.65619500 0.86485000 1.47917000 -0.73547700 -1.40115000 0.08296500 1.63774000 2.02078900 1.57363200 -1.50463400 -1.92081900 -1.52206000 -0.70061900 0.90581500 2.00539900 2.62700000 -1.84067000 -2.53264100 -1.46347000 -0.57213100 0.81513600 1.66206400 2.83097100 -2.66780200 -1.81278000 -1.26577900 0.13147500 1.52742700 2.04799700 2.21472200 4.24349800 -4.08001200 -2.05327400 -2.39801200 -1.32063700 0.14178500 1.61179100 2.63704300
TE D
M AN U
5.00715600 3.77696800 2.34860600 1.71685500 1.66529700 0.34649900 2.41965500 0.28630900 2.31415400 -1.14730800 0.16586000 1.46381200 3.49320000 0.04800300 1.31747500 3.38200500 -2.63979000 -2.58012400 -1.07658000 1.61885700 -1.22211900 1.42676200 -2.45841600 -4.00536400 -3.95352200 -2.34022100 -1.04201600 -1.24978100 -3.76200300 -4.71768400 -4.63555100 -4.60768300 -3.61378000 -1.02201900 -1.02686700 -1.27517600 -1.25299900 -3.91832100 -5.79384600 -6.05421300 -5.67730000 -3.72530000
EP
AC C
C C C C C N C N C Zn C C H C C H N N C H C H C C C C C C C C C C C C C C C H H C H H
S39
ACCEPTED MANUSCRIPT
RI PT
6.84689800 5.64134300 5.50546700 3.04478600 -5.06376800 -2.60301200 -6.40812200 -5.20506600 6.75181700 7.82061800 6.90332300 5.45690200 2.88143300 -6.31114100 -5.01376600 -2.43783700 -7.38262000 -6.46803700 7.66088100 7.51365300 7.47277700 6.62345200 3.34297500 3.30578600 1.80249600 -7.21955300 -2.89176700 -1.35855400 -2.86876200 -7.04059300 -7.07467600 -6.18951400 0.22081900 0.07803000 -1.04525000 0.96756300 -1.21924400 -1.98544300 0.79720800 1.82087700 -0.26183800 -2.30401800 -3.13586600 1.54349700
SC
2.98010500 0.82112200 5.02651700 4.78207500 -4.86451100 -4.61669300 -2.82010600 -0.65980700 4.38064300 2.50328200 0.09433200 6.10971000 6.22925100 -4.22034800 -5.94751800 -6.06341900 -2.34463700 0.06535500 4.97665200 0.33214700 0.30960500 -0.96050900 6.69465500 6.66497500 6.39313100 -4.81750000 -6.53544000 -6.22592700 -6.49340600 -0.14642700 -0.17738500 1.12048300 0.11350400 0.03167800 -0.69169200 0.61577300 -0.79062800 -1.30845000 0.51725500 1.16558600 -0.16292700 -1.49003100 -2.04448200 1.00642900
EP
TE D
M AN U
-0.98767800 -1.03896200 -0.99265500 -1.04793100 -1.30463500 -1.26808500 -1.28251600 -1.22545600 -0.97340600 -0.97209700 -1.01934700 -0.98121200 -1.02751600 -1.30823600 -1.32431600 -1.29966600 -1.28611500 -1.23661300 -0.94684100 -1.90142900 -0.10473700 -1.03898300 -1.90926400 -0.11257500 -1.04714900 -1.33143100 -0.41747500 -1.28964500 -2.21423700 -2.15004900 -0.35327400 -1.21321600 -7.28472000 -8.68421700 -9.26031100 -9.59657800 -10.72454200 -8.52458700 -11.00195600 -9.21133600 -11.62299300 -11.11086000 -9.64874200 -11.62365200
AC C
C O C O C O C O C H C H C C H C H C H H H H H H H H H H H H H H C C C C C N C H C N S H
S40
ACCEPTED MANUSCRIPT
RI PT
0.08096600 1.29922500 -1.16647900 1.26382500 2.57267200 -1.19021100 -2.41188000 0.02220900 2.49863200 3.74274000 2.60164600 -2.45326100 -2.39642900 -3.61039800 -0.00823600 3.70276400 2.46994200 4.69759700 -3.62888700 -2.46882200 -4.54332900 -0.54589200 0.50170200 4.62606400 -4.57413900 -0.42135400 -1.24028300 0.40818700 1.13889000 -0.98165700 0.12083500 -1.78126300 -1.36309400 0.94393800 -0.09054500 1.65489800 1.23747800 -1.67426100 -0.84577900 -2.30438000 1.57964900 0.83301600 2.13369400 -2.29992600
SC
0.01526900 0.12404700 -0.09661300 0.14736800 0.22283600 -0.12150400 -0.19515700 0.01357900 0.32548000 0.37194200 0.16791100 -0.30081200 -0.13909900 -0.34589000 0.01674200 0.43657300 0.36779000 0.44284600 -0.41203100 -0.34440300 -0.41700000 1.16099200 -1.12281500 0.57066400 -0.54745700 2.44608400 1.04085700 -2.41061700 -0.99543100 3.56554300 2.56868900 2.16860800 0.06341900 -3.52538600 -2.53873900 -2.11867200 -0.01597700 3.46051900 4.54369500 2.04725000 -3.41300600 -4.50572400 -1.99167600 4.66597700
TE D
M AN U
6.43289500 7.17431300 7.12359900 8.62216600 6.51755900 8.57165600 6.41510500 9.30277600 9.33891100 7.23985400 5.43390300 9.23711700 5.33126200 7.08873300 10.74536500 8.67037000 10.42134700 6.72486800 8.51964900 10.31978200 6.53506400 11.41853300 11.44704600 9.22816700 9.03905700 10.84411100 12.64646200 10.87268300 12.70498400 11.47536400 9.91138400 13.27719800 13.10293800 11.53294400 9.91672300 13.36400400 13.16294500 12.70564700 11.02003600 14.21883300 12.79295300 11.07551700 14.32822500 13.31826900
EP
AC C
C C C C C C C C C C H C H C N C H H C H H C C H H C C C C C H C H C H C H C H H C H H C
S41
ACCEPTED MANUSCRIPT
RI PT
-2.90231800 -2.32133600 -3.49893400 -2.92891000 -2.91019000 -3.49883600 -3.95369100 -2.92926200 2.18432000 2.14464000 2.83007200 2.71921100 3.41275700 2.90338100 3.35300800 2.69338500 3.90317300 -0.40323500 0.85091400 -1.40097000 -0.05813800 -1.19755100 -2.22138500 0.03849700 -1.91766700 -1.04650400 1.13103800 -2.06219800 -3.25832000 -1.05194400 0.04262200 -1.80719100 0.27004200 1.28054400 -0.48354500 1.20757500 2.37297600 0.31142600 2.26411100 3.27219000 2.19000600 -4.05852600 3.89364500 1.48980500
SC
5.64133800 4.91522400 6.81239600 5.46703300 6.07520300 7.02286500 7.52042500 6.27978500 -4.61276800 -4.85730800 -5.58612800 -6.01043100 -6.75073000 -5.41513200 -6.95618500 -6.21098400 -7.45747800 -0.24225600 0.55696800 -0.86692200 -0.00565000 -0.72721700 -1.38967000 0.06547400 -1.16963200 -0.61363300 0.76104000 -2.58857800 -0.67985400 -0.60706100 0.08530700 -1.07791500 0.23737300 0.87505100 -0.23044100 0.83909800 1.55495700 0.28270700 1.50420900 2.11451000 1.46416400 8.13320100 -8.05923800 -3.90262000
EP
TE D
M AN U
12.49768900 14.72500600 13.00108100 11.42527300 15.25115100 14.39079400 12.31683700 16.31523300 13.43705900 14.84424800 12.64767600 15.40046100 13.18147300 11.57692700 14.57064400 16.46516500 12.52092600 -13.06283000 -14.15734200 -13.82372100 -15.57465400 -15.21147200 -13.35030200 -17.00884600 -16.47493900 -17.58701400 -18.21447500 -16.55310500 -16.53781700 -18.98767500 -19.54453700 -19.60736400 -20.94013000 -21.63660100 -21.57658000 -23.11497200 -21.01280400 -23.77984700 -23.71261100 -20.48260400 -24.69271200 15.02997300 15.23827100 15.62826300
AC C
C C C H C C H H C C C C C H C H H C S C C C H C C C S F F C C H C C H C C O O N H O O O
S42
ACCEPTED MANUSCRIPT -1.71042500 1.30870000 2.27347000 0.74826300 0.73316200 4.56954900 5.43847000 3.88442500 4.90198200 -4.69015000 -5.53952600 -3.97014200 -5.04611700 -1.58935800 -2.57558500 -1.02682800 -1.03998900
RI PT
3.95797600 -4.15833900 -4.20962100 -5.08819300 -3.30808100 -9.08118600 -8.66568100 -9.54434900 -9.82920400 9.15790100 8.74833300 9.61137600 9.91226600 4.21828700 4.28237000 5.14292400 3.36368500
SC
15.54077900 17.05014800 17.57363300 17.21790400 17.42204500 14.45171600 13.92256700 13.72805100 15.17438200 14.21090500 13.64656000 13.51549300 14.91554500 16.96822800 17.44855300 17.15656000 17.36864400
AC C
EP
TE D
M AN U
O C H H H C H H H C H H H C H H H
S43
ACCEPTED MANUSCRIPT FSQ104
SC
RI PT
0.42216300 -0.25673900 0.50169800 -0.26958100 0.50798800 -0.25252800 1.69059100 -0.67272200 -0.68548300 0.18956000 1.86597700 -0.71795900 2.90379500 -1.12089600 -0.88484600 0.28050600 -1.88625300 0.61501700 0.47605300 -0.19467400 3.16075900 -1.18299200 3.80974100 -1.43582500 3.03538100 -1.18170700 -2.18269800 0.75250600 -2.80793800 0.96163400 -1.99230400 0.63917200 -0.91223300 0.32590400 1.83932400 -0.66956500 3.76158800 -1.38096800 4.81900400 -1.80299500 -2.80610400 0.99314400 -3.81494200 1.32467500 -2.21207600 0.79294100 -0.74279100 0.27900500 1.64243600 -0.57931300 3.14396600 -1.14049300 5.17679700 -1.88728900 -4.22027900 1.50197900 -2.86061400 1.04096300 -1.95953900 0.72500700 0.44390700 -0.14097300 2.84681800 -1.00091100 3.77011900 -1.34580900 6.26881200 -0.98969900 5.45342600 -3.27288700 -4.49358100 2.88835900 -5.31414600 0.60654100 -3.87008100 1.40736900 -2.09507000 0.78378900 0.41065700 -0.11455200 2.96044100 -1.02533600 4.77809200 -1.70522000
TE D
M AN U
6.00361400 4.77777600 3.35116600 2.67861400 2.71285700 1.30159800 3.33864400 1.34097100 3.41365400 -0.14129200 1.07438000 2.34971000 4.40924200 1.15428700 2.45068100 4.48961500 -1.58281200 -1.62452500 -0.19137200 2.46790200 -0.09342300 2.59774500 -1.35251500 -2.95511900 -2.99096600 -1.43237500 -0.20952400 -0.06919200 -2.63268100 -3.62249800 -3.62922800 -3.68982800 -2.72971200 -0.17676800 -0.25829100 -0.02708300 -0.09063600 -2.75163900 -4.69414400 -5.04685900 -4.76400100 -2.87905900
EP
AC C
C C C C C N C N C Zn C C H C C H N N C H C H C C C C C C C C C C C C C C C H H C H H
S44
ACCEPTED MANUSCRIPT
RI PT
-1.45439400 0.35934200 -3.75754500 -4.09846000 3.37605200 3.71129500 1.07418900 -0.74353300 -2.83726800 -0.76254000 1.36246700 -4.82122700 -5.54211400 2.45787500 4.44045100 5.15611300 0.38402500 -1.74400700 -3.20236100 1.31803800 1.24532300 2.32071900 -5.83876400 -5.91184600 -5.95565200 2.82529600 5.46970600 5.56735700 5.51182900 -1.62471500 -1.69879700 -2.70351200 -0.06993100 0.00952800 0.46466500 -0.33006400 0.55413100 0.82834800 -0.24293500 -0.67449600 0.18507800 0.99093900 1.30185600 -0.53127100
SC
7.60269600 5.92227000 6.78030700 4.33071300 -5.81929300 -3.36883300 -6.64695600 -4.97060100 7.84000800 8.43725100 6.97729300 6.98730200 4.51353800 -6.88108800 -6.02377800 -3.54795000 -7.48308100 -6.02785900 8.86416300 7.60481000 7.60360200 6.45608000 5.04882400 5.05234400 3.50350400 -7.90441500 -4.07939700 -2.53688300 -4.08875700 -6.65223400 -6.65689400 -5.50891000 0.31532600 0.11794900 -1.15877200 1.09251500 -1.39267700 -2.19499500 0.86328100 2.06087500 -0.34263500 -2.62065600 -3.51669000 1.68424400
EP
TE D
M AN U
-0.19364700 -0.12823700 -0.27569100 -0.28642300 -0.00647100 -0.00916100 -0.07035700 -0.13265200 -0.24314900 -0.16965300 -0.08713100 -0.31309500 -0.34522200 -0.02863200 0.02392600 0.02577400 -0.08768500 -0.17610200 -0.25663400 -0.98791900 0.80795700 -0.04875900 -1.25771100 0.53805800 -0.36006100 -0.01420100 0.93490500 0.03015000 -0.86196400 -1.07220700 0.72367900 -0.21428400 -6.27470000 -7.66721500 -8.19685500 -8.61628000 -9.65353300 -7.42265200 -10.01361300 -8.26629500 -10.59096100 -9.99492500 -8.49883200 -10.66604100
AC C
C O C O C O C O C H C H C C H C H C H H H H H H H H H H H H H H C C C C C N C H C N S H
S45
ACCEPTED MANUSCRIPT
RI PT
-0.22839400 -0.65444900 0.22406600 -0.64420300 0.25932600 -0.16699500 -0.12945600 -0.72257100 0.56030000 -1.92173000 -0.12955800 1.72723200 0.07995800 -2.50146900 -2.40343600 -0.71889800 0.79642000 2.39135700 2.11635000 0.74997300 -0.83325200 -1.91587200 -3.43658300 -0.22635300 1.92565400 3.29741600 0.33660600 -1.01429500 0.61984600 -2.53774100 -3.53728300 -2.03345700 -3.92381900 -3.98431800 -3.23462500 -4.69161700 2.61298100 2.49046800 3.81543000 3.31271400 1.84484300 4.09291900 3.32661900 -3.36261700
SC
0.29965700 1.36242700 -0.90236200 1.24854600 -1.00708000 0.05372700 -0.08994900 -1.24450800 0.88515300 -1.78732400 -1.88176000 1.50942300 1.26310500 -2.92441900 -1.30207200 -3.01745200 -1.49314200 2.48142500 1.22833800 2.22978600 0.81708700 -3.57309000 -3.29528700 -3.49172900 2.86458100 2.93135500 2.52081200 2.26742300 -1.90851400 -4.76737100 -5.57172100 -5.39447700 -6.67104100 -5.40255500 -6.74815500 -7.38756900 3.87592900 4.14258500 5.02942400 5.22441100 3.56750000 5.82139800 5.54295200 -7.75088700
TE D
M AN U
7.42107500 8.25622500 8.03613700 9.65376100 9.43392800 10.26066200 11.68304500 12.28294800 12.47172800 11.76048600 13.39839700 11.97971600 13.74730600 12.33227800 10.91679400 13.96816000 13.81083100 12.73925300 11.00520400 14.50288200 14.12931900 13.45127800 11.92135400 14.81408800 14.02061700 12.33938200 15.46493700 7.77941100 9.91641200 14.03421300 13.51874300 15.67140800 14.36512100 12.54523400 15.55491100 14.09105500 14.83177600 16.18264800 14.08821800 16.66109600 16.83744200 15.69617400 17.69862000 16.66700400
EP
AC C
C C C C C C N C C C C C C C H C H C H C H C H H C H H H H C C S C H C H C C S C H C H C
S46
ACCEPTED MANUSCRIPT
RI PT
-4.14379400 -3.63477200 -2.42705900 5.06773700 4.79706800 6.08888500 5.08481300 0.25601100 -0.22676400 0.65402600 0.14059000 0.58485700 0.97207000 0.11241500 0.87592700 0.54135400 -0.30848600 2.23007700 0.10594000 0.55154300 0.12565500 0.85096800 0.04426800 -0.34832600 0.34352100 -0.31193300 -0.77986500 0.04328500 -0.72376900 -1.13508300 -0.68924600 0.62707500 -1.10189400 1.09259600 0.30823100 1.99274700 1.33239300 -1.53743600 -2.41292400 -0.72702700 -1.80758200
SC
-8.47969900 -7.27471900 -8.30294300 6.95768700 7.80691000 6.65410100 7.31322300 -0.54162600 0.82415600 -1.67661400 -0.23101800 -1.49036400 -2.57806000 -0.16683600 -2.32969400 -1.39338400 1.01319200 -2.78289900 -3.53248300 -1.44203200 -0.23994400 -2.30214800 -0.02957900 1.07318700 -0.88706800 0.94693000 2.30725400 -0.06944800 2.10331000 3.32375500 1.99077700 -1.91990900 2.23696700 -3.17836600 -3.65389100 -3.02736100 -3.81085500 3.51169200 3.38392100 4.00051100 4.11999800
EP
TE D
M AN U
16.42107600 17.61869700 16.83036800 15.82798300 15.18594700 15.55985400 16.86496400 -12.02416000 -13.16949000 -12.74428200 -14.54927900 -14.13959200 -12.23762200 -15.98645900 -15.37314600 -16.52033100 -17.23603400 -15.41736300 -15.40909700 -17.91998500 -18.52136500 -18.50876200 -19.92528600 -20.66237200 -20.53113100 -22.13689400 -20.08305000 -22.76595100 -22.77677600 -19.58970500 -23.75341100 7.16908900 10.52306500 7.74009200 8.34441200 8.35150800 6.88335000 9.97072000 9.31861100 9.41272100 10.83565700
AC C
H H H C H H H C S C C C H C C C S F F C C H C C H C C O O N H O O C H H H C H H H
S47
ACCEPTED MANUSCRIPT SM315
RI PT
0.01533000 -0.93664200 0.89764000 -1.14244300 -1.86611000 0.94816400 1.90873700 -0.18035400 -2.17342000 -2.62238600 -1.92170300 1.95981400 2.55799200 2.08797900 0.79859100 -1.32766100 -2.71810800 -3.41331300 2.36316600 3.36914000 1.81634400 0.57414600 -1.26081400 -2.31709000 -3.81338200 3.46750300 2.22915100 1.46674800 -0.38214600 -2.22921200 -2.87805700 -3.51053700 -5.17310800 4.81940400 3.18295200 2.99932800 1.49779100 -0.45094700 -2.38242000 -3.66073600 -4.52987500 -2.15230100
SC
0.03904200 -0.86091800 0.84853500 -1.11284600 -1.65471000 0.91545900 1.72848800 -0.19549700 -2.04536500 -2.38696900 -1.65470000 1.81506100 2.32612000 1.86883400 0.70361000 -1.29005200 -2.57478400 -3.08694400 2.17507000 3.03871900 1.66015100 0.48255700 -1.24763600 -2.22256700 -3.59516700 3.18693600 2.03985000 1.31756500 -0.42522200 -2.17507400 -2.77438300 -4.97143600 -3.20862400 2.78279100 4.57154600 2.76281200 1.33968300 -0.50480900 -2.33722200 -3.51827200 -5.94012100 -5.28149100
EP
TE D
M AN U
-3.16256100 -2.62984100 -2.41106300 -1.27539700 -3.41823800 -1.02035400 -2.97604800 0.30876900 -1.19045800 -2.53183600 -4.49662800 -0.69567900 -1.91998800 -4.03160700 1.89074700 1.63656300 0.00332900 -2.75957500 0.61264200 -1.96094200 1.80191600 3.23952400 3.01922800 1.30536500 -0.13357400 0.73935300 3.14668800 4.03444600 3.78211200 3.58488000 2.53007400 -0.25253800 -0.15373000 0.82827900 0.77449200 3.37400200 5.11564700 5.20089500 4.64207100 2.57031900 -0.38868500 -0.22297300
AC C
C C C N C N C Zn C C H C C H N N C H C H C C C C C C C C C C C C C C C H H C H H C O
S48
ACCEPTED MANUSCRIPT
RI PT
-6.20714600 -5.40001800 5.86312700 5.02866700 4.21222600 1.83130900 -5.86902300 -4.29229200 -1.73802300 -7.24855100 -6.76928800 5.54297900 6.89840400 6.38615100 3.98878300 1.43921100 -6.65944800 -2.12795100 -2.06159000 -0.64762300 -7.34840200 -7.27126700 -6.68054900 6.34090300 7.01515600 6.28297200 6.84273000 1.73270200 1.87346600 0.35105100 -0.46198700 -0.41196900 0.52179600 -1.22449400 0.58784500 1.37279200 -1.14848200 -1.94638600 -0.27256000 1.50146900 2.30053400 -1.84364900 -0.24401300 0.19181500
SC
-4.16187200 -1.83800100 3.72688800 1.40503400 5.53147900 4.89936100 -5.51946600 -6.99421300 -6.66953800 -3.86005600 -1.34300900 5.09332600 3.41151600 0.89065200 6.59221800 6.30115900 -6.25895600 -7.29127300 -7.08053800 -6.64602900 -1.75277400 -1.58040900 -0.26045200 5.82607600 1.23933300 -0.19503000 1.17800700 6.77779900 6.85354300 6.29303200 -0.52753600 -0.49494000 0.39246900 -1.27301700 0.45017400 1.20294500 -1.21698000 -1.94256600 -0.39625700 1.32142500 2.08104100 -1.84107500 -0.40506700 0.71662300
TE D
M AN U
-0.28811000 -0.03511400 0.95105900 0.78313700 0.89663900 0.68234400 -0.40421800 -0.47986400 -0.37067900 -0.30381900 -0.04636800 0.98366500 1.01856700 0.89568600 0.92385000 0.71066200 -0.50848700 0.44716400 -1.33685700 -0.32753700 0.79270200 -0.99452800 0.06209000 1.07778500 0.06488700 0.84857700 1.85282900 1.65618700 -0.13411100 0.62480500 6.43103400 7.84387100 8.51898100 8.67062600 9.99733400 7.86683100 10.09404300 8.21248800 10.80752700 10.47568500 9.09128000 10.64777000 12.29182800 13.04484200
EP
AC C
C O C O C O C H C H C C H C H C H H H H H H H H H H H H H H C C C C C N C H C N S H C C
S49
ACCEPTED MANUSCRIPT
RI PT
-0.67600300 0.16934500 0.55282800 -0.69596300 -0.96760700 -0.27810600 0.49752600 -1.02030300 -0.31561100 -0.69225400 0.12368100 0.07949600 0.09198700 0.68671000 -0.42997200 1.71206800 0.24452700 -1.53212300 0.15052000 2.27559900 2.06043500 0.82071100 -0.55412900 -2.02618900 -2.00578100 -0.36106500 1.00870000 1.85608600 3.04364300 0.45470800 -1.45883200 -2.89223700 0.10245900 2.52856200 -1.97972200 1.84077500 3.91665500 -2.40609200 -2.09212100 2.51992500 0.46135700 4.62010800 4.47458400 -2.92510900
SC
-1.55676900 0.69861900 1.59594900 -1.57939900 -2.45260100 -0.44669300 1.56512000 -2.46453700 -0.50951800 -1.48272900 0.66436000 0.57222600 0.14264300 -0.92935900 1.31683900 -1.71094600 -1.26855100 1.99738600 1.84927000 -2.78353000 -1.48389800 -2.33715100 -0.69736400 3.16875800 1.60402400 3.01218900 1.35773400 -3.12131000 -3.37988300 -2.57854100 3.70847700 3.65159000 3.39351500 -4.22535700 4.98413800 -5.13054000 -4.42683900 6.01601200 5.23805600 -6.16383800 -4.94533200 -5.45570500 -3.73734500 7.24105700
TE D
M AN U
13.00637800 14.44552900 12.52690300 14.40347200 12.46616200 15.13812600 15.00967100 14.94308100 16.61622300 17.29712200 17.22499200 18.20326900 -4.60503400 -5.34154300 -5.23376900 -4.76151100 -6.64372400 -4.66747500 -6.41068100 -5.46677200 -3.75869100 -7.34219600 -7.10709800 -5.25783700 -3.77338100 -7.00066000 -6.85886500 -6.77612300 -4.97978300 -8.33344800 -6.43755900 -4.81093800 -7.90333300 -7.51791600 -7.00445500 -8.38381000 -7.37515700 -6.14360100 -8.40633600 -9.04779300 -8.51731200 -8.02907400 -6.74716900 -6.60308600
EP
AC C
C C H C H C H H C O O H N C C C C C C C H C H C H C H C H H C H H C C C C C C C O C H C
S50
ACCEPTED MANUSCRIPT
RI PT
-2.30547300 -2.60599700 -1.68463700 3.90779300 2.00984000 -0.31289500 5.69060500 -3.02260700 -3.22822000 -2.70145200 -1.89073700 4.47414400 -0.20317800 -0.01945800 -1.35055000 -3.51280000 -1.30219700 -2.95343000 -1.54519800 5.90437600 -3.96413700 6.48513100 6.11414200 6.17537600 -4.30472600 -3.14364900 -4.79623900
SC
5.86598800 6.45149000 4.21212100 -6.32725300 -6.85991400 -5.91525200 -5.55131800 7.45192600 7.99843600 6.65518400 4.36429600 -7.38795100 -6.92554200 -5.92064400 -5.58774900 8.61762700 5.20041000 4.51514800 3.42616000 -7.62449300 9.69949700 -6.76012800 -8.48984500 -7.85159100 10.48619700 10.07858300 9.37639900
TE D
M AN U
-5.07198400 -8.88912700 -9.26437700 -8.87070300 -9.70339600 -9.27819800 -7.88307900 -7.98917800 -5.88825100 -9.94928200 -10.69754800 -9.58526200 -8.86067200 -10.33724000 -9.18581600 -8.58696400 -11.10015500 -10.93191600 -11.13688300 -9.45285600 -7.72403300 -9.80413100 -10.08497600 -8.41229500 -8.40042700 -7.09879300 -7.08292300
AC C
EP
H C O C H C H C H H C O H H H O H H H C C H H H H H H
S51
ACCEPTED MANUSCRIPT The Cartesian Coordinates of dye-TiO2 complexes F101-TiO2
RI PT
11.85840000 11.94230000 12.02050000 12.17380000 11.81810000 12.32260000 11.87580000 12.53380000 12.19910000 11.97100000 11.62980000 12.36970000 12.09560000 11.64080000 12.86290000 12.77720000 12.42800000 11.94080000 12.63320000 12.06970000 12.86720000 13.12840000 13.04860000 12.69040000 12.38480000 12.66370000 13.14610000 13.30770000 13.21800000 13.13890000 12.91870000 11.16940000 13.55290000 11.49980000 13.85920000 13.20980000 13.52880000 13.49770000 13.34330000 12.90740000 11.11360000
SC
11.93610000 10.94330000 11.73780000 9.60120000 11.18360000 10.52930000 12.76410000 8.71010000 8.98810000 9.97140000 12.14850000 10.76790000 12.16230000 13.80510000 7.81590000 6.89730000 7.61630000 9.75950000 9.80430000 12.61850000 8.43980000 6.48880000 5.68850000 6.65380000 7.15630000 10.27530000 7.46350000 6.25310000 5.48020000 4.65070000 5.24930000 6.75380000 7.12620000 10.25170000 10.74570000 7.68200000 5.28900000 4.17230000 3.60520000 4.78550000 6.33610000
TE D
M AN U
7.61960000 8.61860000 6.23270000 8.38500000 10.03830000 5.63500000 5.22500000 6.56780000 9.62370000 10.65840000 10.49730000 4.27480000 4.01380000 5.41980000 4.75020000 7.50720000 9.85930000 11.72230000 3.27910000 3.02940000 3.50950000 4.51540000 6.91310000 8.87160000 11.28430000 1.85750000 2.47920000 3.09900000 5.51590000 7.91410000 9.12660000 11.87470000 12.07270000 1.06270000 1.27740000 1.41810000 2.64890000 5.06170000 7.70720000 10.10770000 13.21580000
EP
AC C
C C C N C N C Zn C C H C C H N N C H C H C C C C C C C C C C C C C C C H H C H H C
S52
ACCEPTED MANUSCRIPT
RI PT
10.07140000 13.51550000 14.70220000 11.52240000 10.36890000 13.90040000 14.95530000 12.29190000 10.17390000 8.79960000 14.41840000 15.92070000 12.72680000 10.62260000 9.16120000 14.82580000 16.20420000 12.25610000 8.80430000 8.53360000 8.08050000 16.16570000 15.85000000 16.69190000 12.75140000 8.85370000 8.40670000 9.28620000 16.52140000 16.13290000 16.92300000 13.74260000 14.02100000 14.11540000 14.21990000 14.40120000 13.94880000 14.49600000 14.15800000 14.59910000 14.45440000 14.15040000 14.63440000 11.58440000
SC
6.80630000 6.71190000 7.53610000 10.67860000 9.78210000 11.17660000 10.73760000 6.32180000 6.02680000 6.43500000 6.69290000 7.52940000 11.13720000 10.65710000 9.70860000 11.53610000 11.19990000 5.99910000 5.38520000 7.09340000 6.56360000 6.51370000 8.21300000 7.88120000 11.46970000 10.70530000 9.30760000 9.02950000 10.57000000 12.25050000 11.10960000 3.05840000 1.82590000 1.74120000 0.63230000 0.46760000 2.79110000 -0.59060000 0.64890000 -0.74080000 0.53750000 2.17750000 -1.46600000 13.27890000
TE D
M AN U
11.04270000 13.41560000 11.42960000 -0.27630000 1.69770000 -0.06000000 2.11400000 13.96870000 13.66750000 11.60980000 14.02150000 12.19860000 -0.81930000 -0.88650000 0.91500000 -0.50420000 1.56390000 15.00990000 11.93980000 12.45030000 10.79500000 12.54420000 13.05820000 11.50620000 -1.85790000 0.56380000 1.59880000 0.05850000 0.71940000 1.24420000 2.38450000 4.59890000 3.98670000 2.54430000 4.68900000 1.87800000 1.73760000 4.04280000 5.77640000 2.65470000 0.54350000 0.15330000 4.67860000 8.05760000
EP
AC C
O C O C O C O C H C H C C H C H C H H H H H H H H H H H H H H C C C C C N C H C N S H N
S53
ACCEPTED MANUSCRIPT
RI PT
10.28360000 12.62740000 9.16460000 10.07710000 13.96550000 12.36170000 7.88510000 9.30100000 8.79220000 10.92810000 14.99730000 14.19400000 13.40000000 11.33610000 7.65900000 7.04310000 8.66440000 14.74740000 16.02050000 13.16370000 6.27560000 15.87680000 5.91370000 5.23310000 17.06340000 15.84790000 4.58990000 6.93180000 3.89910000 5.48210000 18.17910000 17.10690000 16.94710000 14.69150000 3.58340000 4.30090000 6.56280000 3.14090000 18.11130000 19.06500000 16.93820000 14.69030000 2.31480000 5.84160000
SC
13.59220000 14.24050000 12.89860000 14.56600000 13.84290000 15.59920000 13.18350000 12.12950000 14.84760000 15.10500000 14.77750000 12.80090000 16.52690000 15.92750000 14.16910000 12.61030000 15.60290000 16.14220000 14.44330000 17.56740000 14.48570000 17.09200000 14.79300000 14.48330000 16.68360000 18.42850000 15.07200000 14.77410000 14.76010000 14.28190000 17.51650000 15.67530000 19.27870000 18.82530000 15.05580000 15.30020000 14.96210000 14.75350000 18.82380000 17.14330000 20.29940000 20.13490000 15.35180000 14.19600000
TE D
M AN U
8.53100000 7.99650000 8.03080000 9.53030000 8.18040000 7.72790000 8.50860000 7.27160000 9.99300000 9.94570000 8.09410000 8.40240000 7.66130000 7.56140000 9.49250000 8.11920000 10.76490000 7.83620000 8.26950000 7.44940000 9.92120000 7.70220000 11.26380000 8.97840000 7.07030000 8.19350000 11.61270000 12.19890000 9.30300000 7.93620000 6.91290000 6.65770000 8.04750000 8.83850000 10.63350000 12.63570000 13.57900000 8.52260000 7.40770000 6.40380000 8.42180000 9.43970000 11.09640000 13.90160000
EP
AC C
C C C C C C C H C H C H C H C H H C H H C C C C C C C O C H C H C O C H C H C H H C O H
S54
ACCEPTED MANUSCRIPT
RI PT
6.14290000 7.49740000 19.12870000 14.78840000 15.49760000 13.71770000 1.25430000 20.34160000 1.42690000 0.34730000 1.14950000 21.00800000 20.15190000 20.80020000 14.87810000 15.10050000 15.01220000 15.36300000 15.28410000 14.91000000 15.64380000 15.52370000 15.74870000 15.88660000 14.43990000 16.62230000 16.02480000 16.13570000 16.14620000 16.41770000 16.61160000 16.46640000 9.55040000 9.50740000 9.08040000 9.45880000 19.18200000 19.35410000 19.41300000 19.19970000 19.26190000 19.25340000 19.24460000 13.88680000
SC
15.96560000 14.85320000 19.75520000 20.92280000 20.22900000 20.21840000 15.34020000 19.32450000 16.09470000 15.58840000 14.34480000 20.19220000 19.04380000 18.48050000 -2.01440000 -3.47650000 -2.34860000 -4.45960000 -3.71190000 -1.60180000 -5.83600000 -4.63030000 -5.98010000 -7.34070000 -4.63980000 -4.22070000 -7.28960000 -8.16460000 -7.62310000 -9.58680000 -10.22670000 -10.15020000 -15.52820000 -15.69260000 -16.38240000 -15.63970000 -15.91050000 -15.45710000 -15.43200000 -12.16490000 -11.50740000 -11.63500000 -11.77560000 -16.61070000
TE D
M AN U
13.74560000 14.13890000 7.31850000 8.67760000 10.18140000 9.93550000 10.12050000 6.67010000 9.33850000 10.68100000 9.66280000 6.70540000 5.62300000 7.20730000 2.03190000 3.07120000 0.68220000 1.65790000 0.48920000 -0.09970000 1.33750000 -0.69150000 -0.04720000 2.17550000 -1.58580000 -1.46650000 -0.46560000 0.61050000 -1.49350000 0.55890000 -0.49810000 1.81810000 -2.34760000 0.94360000 4.07240000 7.36100000 -2.71820000 4.19660000 7.43130000 -2.94440000 0.74590000 4.25480000 7.59670000 -4.61880000
EP
AC C
H H O H H H C C H H H H H H C S C C C H C C C S F F C C H C O O Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti
S55
ACCEPTED MANUSCRIPT
RI PT
14.26770000 14.12760000 14.15650000 13.72270000 14.62090000 14.10150000 14.11950000 11.72480000 11.73250000 11.35880000 11.41300000 11.49650000 11.66630000 11.68670000 21.23620000 21.60360000 21.47730000 21.42850000 17.04920000 16.85590000 16.73220000 16.45420000 16.93440000 16.91230000 16.66140000 16.65400000 11.44620000 11.57370000 10.89130000 11.31460000 21.07110000 21.13130000 21.05150000 21.01570000 21.09070000 21.01860000 20.98640000 15.62220000 15.97300000 15.86510000 15.89840000 17.05300000 16.54840000 16.42110000
SC
-17.38590000 -17.24620000 -17.12610000 -13.20540000 -13.77030000 -13.47510000 -13.17570000 -17.25120000 -17.55190000 -17.83520000 -17.57510000 -13.48370000 -13.71640000 -13.90340000 -13.99610000 -12.87750000 -13.46070000 -13.51620000 -15.95720000 -16.26870000 -15.92160000 -15.57000000 -12.57790000 -12.30090000 -12.13570000 -11.87340000 -15.44910000 -15.68460000 -16.07550000 -15.77030000 -15.70000000 -15.29580000 -15.11110000 -12.44430000 -11.13550000 -11.56640000 -11.91360000 -17.06830000 -17.91510000 -17.57990000 -17.41010000 -14.25930000 -14.03460000 -13.91690000
TE D
M AN U
-0.98800000 2.74300000 6.26440000 -4.26720000 -0.87580000 2.72880000 6.34990000 -2.87710000 0.69080000 4.15130000 7.44480000 -2.48980000 0.93160000 7.38700000 -2.23910000 0.88340000 4.14300000 7.52740000 -4.55480000 -0.86770000 2.71700000 6.36080000 -4.64980000 -0.98440000 2.56380000 6.37380000 -2.13950000 0.84610000 4.03710000 6.78530000 -2.83310000 3.88990000 8.34270000 -3.21970000 0.65830000 4.32480000 8.32670000 -5.03520000 -1.21780000 3.06220000 6.38050000 -5.33990000 -0.60930000 2.52690000
EP
AC C
Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti O O O O O O O O O O O O O O O O O O
S56
ACCEPTED MANUSCRIPT
RI PT
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SC
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EP
AC C
O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O
S57
ACCEPTED MANUSCRIPT 11.58130000 12.25970000 12.20020000 22.16310000 22.35680000 22.22370000 17.06360000 16.85470000 17.21620000 17.65790000 17.23190000 17.27040000 17.09990000 17.57190000 16.69750000
RI PT
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AC C
EP
TE D
M AN U
O O O O O O O O O O O O O O H
S58
ACCEPTED MANUSCRIPT F102-TiO2
RI PT
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SC
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TE D
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EP
AC C
C C C N C N C Zn C C H C C H N N C H C H C C C C C C C C C C C C C C C H H C H H C
S59
ACCEPTED MANUSCRIPT
RI PT
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EP
AC C
O C O C O C O C H C H C C H C H C H H H H H H H H H H H H H H C C C C C N C H C N S H N
S60
ACCEPTED MANUSCRIPT
RI PT
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SC
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EP
TE D
M AN U
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AC C
C C C C C C C H C H C H C H C H H C H H C C C C C C C O C H C H C O C H C H C H H C O H
S61
ACCEPTED MANUSCRIPT
RI PT
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EP
TE D
M AN U
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AC C
H H O H H H C C H H H H H H C C S C H C Si C C C C S C C C C C C H C H C H C H C H C C H
S62
ACCEPTED MANUSCRIPT
RI PT
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EP
AC C
H C H H O O H H Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti
S63
ACCEPTED MANUSCRIPT
RI PT
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M AN U
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EP
AC C
Ti Ti O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O
S64
ACCEPTED MANUSCRIPT
RI PT
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M AN U
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EP
AC C
O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O H
S65
ACCEPTED MANUSCRIPT F103-TiO2
RI PT
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TE D
M AN U
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EP
AC C
C C C N C N C Zn C C H C C H N N C H C H C C C C C C C C C C C C C C C H H C H H C
S66
ACCEPTED MANUSCRIPT
RI PT
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M AN U
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EP
AC C
O C O C O C O C H C H C C H C H C H H H H H H H H H H H H H H C C C C C N C H C N S H N
S67
ACCEPTED MANUSCRIPT
RI PT
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TE D
M AN U
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EP
AC C
C C C C C C C H C H C H C H C H H C H H C C C C C C C O C H C H C O C H C H C H H C O H
S68
ACCEPTED MANUSCRIPT
RI PT
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SC
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TE D
M AN U
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EP
AC C
H H O H H H C C H H H H H H C S C C C H H C O O Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti
S69
ACCEPTED MANUSCRIPT
RI PT
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SC
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TE D
M AN U
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EP
AC C
Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti O O O O O O O O O O O O O O O O O O O O O O O O O O
S70
ACCEPTED MANUSCRIPT
RI PT
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SC
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TE D
M AN U
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EP
AC C
O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O
S71
ACCEPTED MANUSCRIPT 5.59990000 -13.00570000 8.67330000 -13.18590000 -2.02980000 -10.33490000 1.61280000 -9.26300000 5.30830000 -9.37680000 9.01330000 -9.34520000 5.31590000 -8.36790000
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AC C
EP
TE D
M AN U
SC
RI PT
O O O O O O H
S72
ACCEPTED MANUSCRIPT F104-TiO2
TE D
M AN U
SC
RI PT
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EP
AC C
C C C N C N C Zn C C H C C H N N C H C H C C C C C C C C C C C C C C C H H C H H C
S73
ACCEPTED MANUSCRIPT
RI PT
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TE D
M AN U
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EP
AC C
O C O C O C O C H C H C C H C H C H H H H H H H H H H H H H H C C C C C N C H C N S H N
S74
ACCEPTED MANUSCRIPT
RI PT
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TE D
M AN U
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EP
AC C
C C C C C C C H C H C H C H C H H C H H C C C C C C C O C H C H C O C H C H C H H C O H
S75
ACCEPTED MANUSCRIPT
RI PT
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TE D
M AN U
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EP
AC C
H H O H H H C C H H H H H H C S C C C H C H C S C H C H C O O Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti
S76
ACCEPTED MANUSCRIPT
RI PT
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TE D
M AN U
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EP
AC C
Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti O O O O O O O O O O O O O O O O O O O
S77
ACCEPTED MANUSCRIPT
RI PT
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TE D
M AN U
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EP
AC C
O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O
S78
ACCEPTED MANUSCRIPT 12.22780000 12.17230000 22.13920000 22.33310000 22.20060000 17.04560000 16.84310000 17.20560000 17.65410000 17.20030000 17.25320000 17.06490000 17.53580000 16.72090000
RI PT
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AC C
EP
TE D
M AN U
O O O O O O O O O O O O O H
S79
ACCEPTED MANUSCRIPT F105-TiO2
TE D
M AN U
SC
RI PT
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EP
AC C
C C C N C N C Zn C C H C C H N N C H C H C C C C C C C C C C C C C C C H H C H H C
S80
ACCEPTED MANUSCRIPT
RI PT
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SC
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TE D
M AN U
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EP
AC C
O C O C O C O C H C H C C H C H C H H H H H H H H H H H H H H C C C C C N C H C N S H N
S81
ACCEPTED MANUSCRIPT
RI PT
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SC
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TE D
M AN U
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EP
AC C
C C C C C C C H C H C H C H C H H C H H C C C C C C C O C H C H C O C H C H C H H C O H
S82
ACCEPTED MANUSCRIPT
RI PT
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SC
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TE D
M AN U
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EP
AC C
H H O H H H C C H H H H H H C C S H C C S C C H C O O Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti
S83
ACCEPTED MANUSCRIPT
RI PT
14.07930000 14.09910000 11.72500000 11.73620000 11.36700000 11.42240000 11.47490000 11.64640000 11.67140000 21.22040000 21.58480000 21.45710000 21.41010000 17.04140000 16.84890000 16.72360000 16.44890000 16.90830000 16.89330000 16.63650000 16.62510000 11.43610000 11.56580000 10.88780000 11.31130000 21.06320000 21.12170000 21.04420000 20.99120000 21.06480000 20.98580000 20.95760000 15.62060000 15.97740000 15.87060000 15.90580000 17.03530000 16.53260000 16.39730000 16.19230000 13.73440000 13.84770000 13.40480000 13.20640000
SC
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TE D
M AN U
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EP
AC C
Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti O O O O O O O O O O O O O O O O O O O O O O O
S84
ACCEPTED MANUSCRIPT
RI PT
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TE D
M AN U
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EP
AC C
O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O
S85
ACCEPTED MANUSCRIPT 22.20440000 17.05310000 16.84750000 17.20780000 17.65410000 17.21110000 17.25690000 17.06900000 17.54240000 16.58490000
RI PT
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AC C
EP
TE D
M AN U
SC
O O O O O O O O O H
S86
ACCEPTED MANUSCRIPT FSQ101-TiO2
SC
RI PT
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EP
TE D
M AN U
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AC C
C C C N C N C Zn C C H C C H N N C H C H C C C C C C C C C C C C C C C H H C H H C
S87
ACCEPTED MANUSCRIPT
RI PT
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EP
TE D
M AN U
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AC C
O C O C O C O C H C H C C H C H C H H H H H H H H H H H H H H C C C C C N C H C N S H C
S88
ACCEPTED MANUSCRIPT
RI PT
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TE D
M AN U
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EP
AC C
C C C C C H C H C H C N C C H C C H C H H C C H H H H C H C H C H H C H H H C S C C C H
S89
ACCEPTED MANUSCRIPT
RI PT
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TE D
M AN U
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EP
AC C
C C C S F F C C H C C H C C O O N Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti
S90
ACCEPTED MANUSCRIPT
RI PT
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ACCEPTED MANUSCRIPT
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ACCEPTED MANUSCRIPT
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ACCEPTED MANUSCRIPT
RI PT
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S98
ACCEPTED MANUSCRIPT 22.15090000 22.34370000 22.21210000 17.05980000 16.85410000 17.21250000 17.65700000 17.21290000 17.25360000 17.08270000 17.55410000 16.59330000
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ACCEPTED MANUSCRIPT FSQ103-TiO2
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ACCEPTED MANUSCRIPT
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S102
ACCEPTED MANUSCRIPT
RI PT
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S103
ACCEPTED MANUSCRIPT
RI PT
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S104
ACCEPTED MANUSCRIPT
RI PT
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AC C
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S105
ACCEPTED MANUSCRIPT
RI PT
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S106
ACCEPTED MANUSCRIPT FSQ104-TiO2
RI PT
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S107
ACCEPTED MANUSCRIPT
RI PT
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S108
ACCEPTED MANUSCRIPT
RI PT
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AC C
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S109
ACCEPTED MANUSCRIPT
RI PT
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AC C
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S110
ACCEPTED MANUSCRIPT
RI PT
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AC C
Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti O O O O O O O O O
S111
ACCEPTED MANUSCRIPT
RI PT
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TE D
M AN U
4.62220000 8.62010000 -4.76660000 -0.95700000 3.32790000 6.64560000 -5.05380000 -0.32020000 2.80420000 6.87450000 -2.55220000 1.09350000 4.84220000 8.05670000 -2.24200000 0.96410000 4.82450000 8.41370000 -0.46600000 2.71660000 6.07870000 -4.16750000 -0.96570000 3.04770000 6.18880000 -4.33310000 -0.98030000 2.87030000 6.34790000 -4.83190000 -0.57470000 2.98410000 6.60140000 -4.45650000 -0.87050000 2.75790000 6.82740000 -2.84530000 0.99440000 4.24080000 8.59950000 -2.67020000 1.45270000 8.29430000
EP
AC C
O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O
S112
ACCEPTED MANUSCRIPT 19.33470000 19.76420000 19.40550000 19.54740000 12.23810000 12.24120000 12.12300000 11.26600000 12.00050000 11.54400000 12.22630000 12.17200000 22.13780000 22.33280000 22.20140000 17.04620000 16.84520000 17.20680000 17.65570000 17.19640000 17.24970000 17.06510000 17.53600000 16.70700000
RI PT
-18.22410000 -17.46830000 -17.76760000 -17.84590000 -21.77640000 -22.34360000 -22.53970000 -22.87250000 -16.85400000 -17.15560000 -17.48660000 -17.32500000 -17.90700000 -17.44500000 -17.79680000 -19.77670000 -20.48740000 -19.73990000 -19.93980000 -17.01500000 -15.96180000 -16.11060000 -16.10160000 -15.10830000
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AC C
EP
TE D
M AN U
O O O O O O O O O O O O O O O O O O O O O O O H
S113
ACCEPTED MANUSCRIPT SM315-TiO2
TE D
M AN U
SC
RI PT
1.04780000 11.07290000 11.87660000 -0.13880000 10.41570000 11.48320000 2.15050000 10.48460000 12.53190000 -0.41350000 9.08440000 11.70130000 -1.22120000 11.03120000 10.75340000 2.24690000 9.15390000 12.87350000 3.31740000 11.19770000 12.99200000 0.82110000 7.70020000 12.58840000 -1.64300000 8.83920000 11.12390000 -2.15380000 10.05300000 10.53670000 -1.26580000 12.07370000 10.45280000 3.44390000 9.00800000 13.54360000 4.11730000 10.28010000 13.61830000 3.50890000 12.25720000 12.85150000 2.03980000 6.32850000 13.50410000 -0.59220000 6.24230000 12.27360000 -2.30790000 7.59600000 11.09480000 -3.10530000 10.14150000 10.01930000 3.94160000 7.81040000 14.09370000 5.08010000 10.44780000 14.09220000 3.28710000 6.56680000 14.05320000 1.78150000 4.99650000 13.70160000 -0.51170000 4.92270000 12.64070000 -1.81450000 6.40020000 11.64450000 -3.63770000 7.54760000 10.40910000 5.25650000 7.86840000 14.80550000 3.81850000 5.34130000 14.59840000 2.88760000 4.36310000 14.37900000 0.59150000 4.32190000 13.30680000 -1.70690000 4.22300000 12.24380000 -2.51340000 5.13920000 11.62370000 -4.81930000 7.88800000 11.09980000 -3.72800000 7.17720000 9.05150000 5.29690000 8.02510000 16.20730000 6.47140000 7.74310000 14.10140000 4.78460000 5.24540000 15.08660000 2.93330000 3.31140000 14.65230000 0.52420000 2.94650000 13.61880000 -1.89760000 3.16800000 12.41950000 -3.49560000 4.97940000 11.18800000 -6.06460000 7.86720000 10.44810000
EP
AC C
C C C N C N C Zn C C H C C H N N C H C H C C C C C C C C C C C C C C C H H C H H C
S114
ACCEPTED MANUSCRIPT
RI PT
12.41360000 8.39230000 8.45420000 16.89410000 16.81850000 14.77920000 12.74500000 9.10270000 10.97540000 13.15210000 7.34490000 7.07370000 16.16790000 17.97520000 18.24590000 14.24130000 11.98540000 8.59500000 13.20630000 12.71190000 14.16010000 6.91950000 6.44380000 6.80500000 16.69630000 18.59310000 18.52120000 18.71300000 12.29550000 12.07200000 10.94500000 13.92100000 14.30250000 14.96340000 14.08180000 15.36410000 15.28410000 14.47870000 13.57880000 15.12190000 15.99110000 16.03060000 14.24060000 15.50970000
SC
8.23750000 7.14810000 6.85760000 8.05550000 8.13120000 7.77420000 7.59000000 7.49850000 8.13410000 8.62510000 6.86160000 6.48060000 7.92780000 8.17540000 8.22870000 7.67240000 7.42870000 7.48240000 7.80400000 9.51770000 8.86000000 5.57100000 7.29690000 6.27560000 7.94900000 9.15490000 8.24540000 7.35620000 6.52680000 8.31200000 7.31690000 1.75400000 0.40580000 -0.05990000 -0.55700000 -1.44500000 0.71430000 -1.90300000 -0.25610000 -2.40320000 -1.68310000 -0.26550000 -2.59390000 -3.82140000
TE D
M AN U
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EP
AC C
O C O C O C O C H C H C C H C H C H H H H H H H H H H H H H H C C C C C N C H C N S H C
S115
ACCEPTED MANUSCRIPT
RI PT
15.49300000 15.87240000 15.80330000 15.21860000 16.17750000 15.93340000 16.14430000 15.76250000 16.44920000 16.42020000 16.59390000 16.43600000 11.59010000 12.33440000 10.60100000 13.65610000 11.77170000 9.48860000 10.70560000 14.38590000 14.10510000 12.51530000 10.74320000 8.51770000 9.37900000 9.72540000 11.57450000 13.84520000 15.40140000 12.05560000 8.60420000 7.64790000 9.84690000 14.67820000 7.57320000 14.19000000 16.02900000 7.01670000 7.07400000 15.03280000 12.87350000 16.88970000 16.41840000 6.01780000
SC
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TE D
M AN U
2.28120000 -0.10790000 2.33420000 3.19350000 -0.05370000 -1.06560000 1.17120000 3.28560000 -0.95790000 1.21410000 0.09160000 2.36310000 1.13990000 0.33820000 2.05270000 -0.03020000 -0.14610000 2.32130000 2.73770000 -0.84260000 0.31500000 -0.95070000 0.11060000 3.23250000 1.79330000 3.64440000 2.57310000 -1.31780000 -1.12940000 -1.30310000 3.92280000 3.38890000 4.16910000 -2.13250000 4.91650000 -3.27430000 -1.80610000 5.74030000 5.08610000 -4.02390000 -3.60000000 -2.54150000 -0.91610000 6.68430000
EP
AC C
C C C H C H C H H C O O N C C C C C C C H C H C H C H C H H C H H C C C C C C C O C H C
S116
ACCEPTED MANUSCRIPT
RI PT
7.40160000 6.08140000 7.60330000 16.38150000 14.68130000 12.37270000 17.92450000 5.54720000 5.63790000 5.68270000 7.08530000 17.10580000 12.92510000 12.42420000 11.32560000 4.57400000 7.26100000 6.00870000 7.63270000 18.49010000 3.98110000 18.61360000 18.88200000 19.03730000 3.23140000 4.72900000 3.48790000 9.41950000 9.27450000 8.92020000 9.25870000 19.11150000 19.67030000 19.39010000 19.16740000 19.55920000 20.01790000 19.24180000 13.84580000 14.25610000 13.98080000 14.19060000 13.60740000 14.48990000
SC
12.07720000 15.68450000 16.37110000 17.72900000 18.09620000 17.18330000 17.17930000 14.65910000 12.53420000 16.68800000 17.70080000 18.56570000 16.85650000 18.28010000 16.87120000 15.05460000 18.11970000 17.72990000 18.29090000 18.74820000 14.04030000 19.20530000 19.42820000 17.79370000 14.55520000 13.56890000 13.27030000 -14.31890000 -14.52050000 -15.21640000 -14.54520000 -14.50580000 -13.90510000 -13.70020000 -10.78120000 -10.29700000 -10.06420000 -10.02710000 -15.10800000 -15.89230000 -15.62550000 -15.65680000 -11.71210000 -12.26150000
TE D
M AN U
5.65170000 6.02650000 4.26400000 -3.66210000 -4.90770000 -4.77810000 -2.22590000 6.82590000 7.29790000 6.16190000 4.37320000 -4.47140000 -5.67280000 -4.69090000 -4.85970000 7.70680000 5.37640000 4.14400000 3.63010000 -4.15200000 8.52630000 -3.15730000 -4.91650000 -4.19330000 9.13640000 9.18320000 7.91260000 -2.16700000 1.10340000 4.27960000 7.59400000 -2.49780000 4.57180000 7.71110000 -2.55910000 0.96100000 4.18150000 7.34220000 -4.34260000 -0.68980000 3.00410000 6.41510000 -3.93040000 -0.56300000
EP
AC C
H C O C H C H C H H C O H H H O H H H C C H H H H H H Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti
S117
ACCEPTED MANUSCRIPT
RI PT
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TE D
M AN U
2.85620000 6.42970000 -2.62220000 0.92060000 4.37320000 7.60910000 -2.33460000 0.99660000 7.56030000 -2.04450000 1.05170000 4.32240000 7.73190000 -4.28420000 -0.56550000 3.01440000 6.55900000 -4.17050000 -0.52010000 2.73080000 6.54580000 -1.92940000 1.00630000 4.27880000 6.96830000 -2.72550000 4.31460000 8.71220000 -2.90680000 0.66840000 4.21950000 8.28560000 -4.82130000 -0.84390000 3.42010000 6.59510000 -4.96810000 -0.23420000 3.09900000 6.60830000 -2.54980000 1.12050000 4.80300000 7.91000000
EP
AC C
Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti O O O O O O O O O O O O O O O O O O O O O O O
S118
ACCEPTED MANUSCRIPT
RI PT
13.46340000 13.31540000 13.98790000 13.01620000 8.53120000 8.25700000 8.33690000 18.62630000 18.62120000 18.97080000 19.88390000 18.48270000 18.88260000 19.43350000 19.42770000 13.64700000 14.83050000 13.54190000 14.45410000 15.02800000 14.98990000 14.78560000 14.43780000 9.89020000 9.90370000 9.46110000 9.78270000 9.52370000 9.49260000 9.60580000 19.35010000 20.08900000 19.92860000 19.56670000 12.25360000 12.24870000 12.05570000 11.24620000 11.87630000 11.16570000 11.74560000 11.86810000 22.28130000 22.75110000
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TE D
M AN U
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EP
AC C
O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O
S119
ACCEPTED MANUSCRIPT 22.36460000 17.00870000 17.08630000 17.57930000 17.61410000 17.14620000 17.61440000 16.73810000 17.47760000 16.81910000
RI PT
6.22690000 -11.97870000 -2.51820000 -14.06750000 1.20590000 -14.66480000 5.13720000 -13.93750000 8.06140000 -13.95730000 -2.39450000 -11.22770000 1.23760000 -10.76790000 4.64820000 -9.92950000 7.78530000 -9.76390000 4.42950000 -8.97600000
AC C
EP
TE D
M AN U
SC
O O O O O O O O O H
S120
ACCEPTED MANUSCRIPT The Cartesian Coordinates of TiO2 cluster
RI PT
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SC
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TE D
M AN U
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EP
AC C
Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti O O O O
S121
ACCEPTED MANUSCRIPT
RI PT
21.06060000 21.11530000 21.04840000 20.96750000 21.02200000 20.94920000 20.95170000 15.62520000 15.98550000 15.87730000 15.91290000 17.02510000 16.52750000 16.38150000 16.18500000 13.73800000 13.85680000 13.41300000 13.21350000 13.60330000 13.74390000 14.25170000 13.26070000 8.72800000 8.44070000 8.53860000 18.75650000 18.68320000 18.60080000 19.63160000 18.52580000 18.73270000 18.70650000 18.77480000 13.68510000 14.84460000 14.39990000 14.45990000 15.09250000 15.13090000 14.90590000 14.87910000 9.89730000 9.98500000
SC
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TE D
M AN U
4.00320000 10.71280000 15.16930000 3.63400000 7.51860000 11.16880000 15.16210000 1.80350000 5.61220000 9.89630000 13.21260000 1.51240000 6.23810000 9.38590000 13.41720000 4.01730000 7.66080000 11.40660000 14.62300000 4.32450000 7.52550000 11.37170000 14.96400000 6.09250000 9.27610000 12.63820000 2.39840000 5.60180000 9.60340000 12.74540000 2.23230000 5.58870000 9.41140000 12.89230000 1.73410000 5.99080000 9.54820000 13.15710000 2.10740000 5.69850000 9.31320000 13.35750000 3.71830000 7.55900000
EP
AC C
O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O
S122
ACCEPTED MANUSCRIPT
RI PT
9.52560000 9.79720000 9.68140000 9.86300000 9.85290000 19.33060000 19.74220000 19.38760000 19.54490000 12.24450000 12.24860000 12.12970000 11.26890000 12.00310000 11.55160000 12.24370000 12.17520000 22.12900000 22.31270000 22.18960000 17.05190000 16.84940000 17.20490000 17.65870000 17.19300000 17.21410000 17.06240000 17.53930000
SC
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TE D
M AN U
10.80470000 15.16760000 3.88580000 8.00510000 14.84940000 4.71860000 7.80480000 10.96390000 13.73500000 2.18120000 5.65160000 9.30340000 12.80190000 2.79290000 6.03610000 9.40970000 12.82950000 6.16350000 9.36110000 12.72660000 4.04100000 7.75630000 11.57830000 14.64620000 3.98020000 7.62740000 11.30930000 14.99010000
AC C
EP
O O O O O O O O O O O O O O O O O O O O O O O O O O O O
S123
ACCEPTED MANUSCRIPT
AC C
EP
TE D
M AN U
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Table 1. Calculated electronic transition data in termed of excitation energies (E/eV), band wavelengths (λ/nm), oscillator Strengths (f), and electronic compositions for the dyes in THF using TD-CAM-B3LYP/LANL2DZ on the PCM model.a Dyes E(eV) λ(nm) f Composition F101 1.76(S0→S1) 703 1.5806 H→L(65%) H→L+1(11%) H-1→L(10%) 3.16(S0→S9) 393 1.1076 H-2→L+3(38%) H→L+3(9%) H-2→L+2(9%) H-2→L+1(8%) H→L+2(8%) H-1→L(6%) F102 1.80(S0→S1) 688 1.5197 H →L(67%) H →L+1(10%) H-1→L(10%) H-2→L+2(5%) 3.16(S0→S8) 392 0.9155 H-2→L+2(50%) H→L+1(22%) H-1→L+1(6%) H-1→L+1(5%) 679 1.2013 H→L(66%) F103 1.82(S0→S1) H→L+1(12%) H-1→L(9%) H-2→L+2(6%) 3.19(S0→S8) 389 1.1700 H-1→L+2(45%) H-4→L(12%) H-1→L+1(11%) H→L+1(8%) 685 1.4463 H→L(67%) F104 1.81(S0→S1) H→L+1(11%) H-1→L(9%) H-2→L+2(5%) 3.13(S0→S7) 396 1.7063 H-2→L+2(36%) H→L+3(15%) H-3→L+3(12%) H-1→L+1(8%) H-1→L+3(6%) H→L+1(5%) F105 1.81(S0→S1) 684 1.3446 H→ L(67%) H→L+1(11%) H-1→L(9%) H-2→L+2(6%) 3.16(S0→S7) 392 1.2668 H-2→L+2(38%) H-2→L+1(11%) H→L+1(9%) H-1→L+1(9%) H→L+2(5%) H-4→L(5%) FSQ101 1.60(S0→S1) 773 2.4426 H→L(60%) H→L+1(13%) H-1→L(11%) H-3→L(5%) 2.81(S0→S7) 441 1.0833 H-2→L+3(19%) H→L+1(17%) H-1→L(17%) H-3→L(13%) H-1→L+2(12%) H-1→L+1(6%) FSQ102 1.62(S0→S1) 764 2.3902 H→ L(57%) H→L+1 (13%) H-1→L(12%) H-3→L(6%) 3.07(S0→S8) 403 1.0409 H-2→L+3(41%) H-1→L(31%) H→L+2(11%) H-3→L(5%) FSQ103 1.64(S0→S1) 756 2.4606 H→ L(57%) H→L+1(15%) H-1→L(9%) 3.13(S0→S10) 396 0.9169 H-2→L+2(35%) H→L+3(31%) H-2→L+1(26%) FSQ104 1.64(S0→S1) 757 2.3918 H→ L(58%) H→L+1(13%) H-1→L(10%) H-3→L(7%) 3.07(S0→S8) 404 1.1799 H-2→L+3(42%) H-1→L(32%) H→L+2(11%) SM315 1.91(S0→S1) 651 0.9497 H→L(63%) H→L+1(16%) H-2→L+2(9%) H-1→L(7%) 3.14(S0→S6) 394 1.5582 H-2→L+2(37%) H→L+1(32%) H-4→L(11%) H-1→L(6%) a
Only orbital percentage >5% are reported; where H=HOMO and L=LUMO.
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F101
0.658
4.853
FSQ101
F102
0.604
3.932
FSQ102
F103
0.637
4.541
FSQ103
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0.607
4.171
F105
0.634
4.489
Dyes
EDDsa
qCT (e)
DCT(Å)
0.719
6.269
0.693
5.937
0.658
5.425
FSQ104
0.683
5.739
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0.564
3.734
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ACCEPTED MANUSCRIPT Table 3. The bond length (Å), and adsorption energy (kcal mol-1) of dye-TiO2 complexes calculated by PBE/DNP in the DMol3 module. Ti-O(Å)
Ti-O(Å)
Eads(kcal mol-1)
Dyes
Ti-O(Å)
Ti-O(Å)
Eads(kcal mol-1)
F101 F102 F103 F104 F105
2.152 2.143 2.141 2.137 2.144
2.130 2.125 2.125 2.119 2.126
-16.4 -0.8 -16.2 -16.8 -15.9
FSQ101 FSQ102 FSQ103 FSQ104 SM315
2.139 2.146 2.130 2.139 2.149
2.121 2.118 2.115 2.124 2.124
-17.2 -18.2 -21.5 -17.1 -15.1
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ACCEPTED MANUSCRIPT Table 4. Calculated electronic properties of the isolated dyes and dye-(TiO2)38 complexes.
(mA cm ) 45.03 44.11 42.00 43.71 43.27 52.14 52.01 51.95 51.96 35.69(18.1)a
Edye (eV)
Edye* (eV)
Ginject (eV)
Greg (eV)
∆ECB (eV)
1.51 1.59 1.56 1.58 1.56 1.32 1.35 1.40 1.38 1.64
-5.32 -5.29 -5.33 -5.31 -5.32 -5.23 -5.22 -5.33 -5.28 -5.33
-3.56 -3.49 -3.51 -3.50 -3.51 -3.63 -3.60 -3.69 -3.64 -3.42
0.44 0.51 0.49 0.50 0.49 0.37 0.40 0.31 0.36 0.58
0.32 0.29 0.33 0.31 0.32 0.23 0.22 0.33 0.28 0.33
0.148 0.151 0.147 0.149 0.148 0.153 0.145 0.150 0.157 0.147
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F101 F102 F103 F104 F105 FSQ101 FSQ102 FSQ103 FSQ104 SM315
J scmax
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ACCEPTED MANUSCRIPT Highlights 1. Photophysical properties of porphyrin dyes were systematically studied theoretically. 2. B1 was screened as an excellent π-conjugated bridge candidate for efficient dyes.
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3. FSQ101-104 exhibited enhanced light-harvesting abilities toward the NIR region.
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4. Designed dyes are expected to be promising sensitizers for highly efficient DSSCs.
S0143-7208(17)32372-0
DOI:
10.1016/j.dyepig.2018.03.045
Reference:
DYPI 6630
To appear in:
Dyes and Pigments
Received Date: 24 November 2017 Revised Date:
17 March 2018
Accepted Date: 22 March 2018
Please cite this article as: Fu Y, Lu T, Xu Y, Li M, Wei Z, Liu H, Lu W, Theoretical screening and design of SM315-based porphyrin dyes for highly efficient dye-sensitized solar cells with near-IR light harvesting, Dyes and Pigments (2018), doi: 10.1016/j.dyepig.2018.03.045. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
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Theoretical Screening and Design of SM315-Based Porphyrin Dyes for Highly
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Efficient Dye-Sensitized Solar Cells with Near-IR Light Harvesting
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Yan Fu, Tian Lu, Yongxin Xu, Minjie Li*, Zhen Wei, Huan Liu, Wencong Lu*
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4 Department of Chemistry, College of Science, Shanghai University, Shanghai 200444, P.R. China
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Email:[email protected]; [email protected]
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ACCEPTED MANUSCRIPT Abstract: We screened five π-conjugated bridges and further designed four dyes
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FSQ101-FSQ104 with screened π-linker B1 as bridge, four electron-rich units D1-D4
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as donors and electron-withdrawing cyanoacrylic acid as acceptor, based on
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experimentally synthesized dye SM315 for highly efficient dye-sensitized solar cells
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(DSSCs) using density functional theory (DFT) and time-dependent density
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functional theory (TDDFT) methods. Our theoretical results reveal that designed dyes
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FSQ101-FSQ104 have not only remarkably better light harvesting abilities toward the
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near-infrared (NIR) region with broader light harvesting efficiency (LHE) curves and
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higher maximum short circuit current densities ( J scmax ), but also obviously narrower
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band gaps, larger adsorption energies (Eads), lower exciton binding energies (EBEs),
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larger conduction band energy shifts (∆ECB ) compared to dye SM315. Therefore, the
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designed dyes FSQ101-FSQ104 might have superior performances and could be
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promising sensitizer candidates for highly efficient DSSCs.
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Graphical Abstract
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Keywords: Porphyrin dyes, DFT/TDDFT, D-π-A structure, Vis/NIR, Optoelectronic
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properties
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1. Introduction Dye-sensitized solar cells (DSSCs) have been widely investigated due to low
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manufacturing costs, ease of fabrication, and tunable aesthetic features of color and
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transparency [1-5], since the seminal work was reported by O’Regan and Grätzel with
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the power conversion efficiency (PCE) of 7.1% in 1991 [6]. Generally, such device
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mainly consists of a dye sensitizer, a metal oxide semiconductor (typically TiO2) as a
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photoanode, a redox electrolyte and a counter electrode (cathode) [7]. As one of the
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most crucial components in DSSCs, the sensitizer plays a significant role in light
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capturing and electron injection which impacts on PCE [2]. Over the last two decades,
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ruthenium complexes [8], metal-free organic dyes [9, 10] and porphyrin sensitizers [3,
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11, 12] have been fully investigated.
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Although the PCE of DSSCs based on ruthenium dyes has reached 11% [13] under
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simulated AM 1.5 irradiation (100 mW cm-2), such as dyes N3 and N719 [14], their
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further application might be limited for rarity and environmental concerns [15]. Thus,
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it is still imperative to develop efficient noble-metal-free sensitizers. Among the dyes,
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porphyrin has aroused wide attention due to its structural similarities to chlorophylls
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in natural photosynthetic systems, as well as its exceptional photophysical properties
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and electrochemical stabilities [16, 17].
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Benefitting from its heterocyclic macrocycle with a π-aromatic core, porphyrin
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shows an intense Soret band (B band) at 350-500 nm and a moderately weak Q band
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at 550-700 nm in the visible region [18, 19]. In general, porphyrin-based dyes employ
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the donor-π bridge-acceptor (D-π-A) structure. It has been revealed that the
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photophysical and electrochemical properties of porphyrins and the efficiencies of 4
ACCEPTED MANUSCRIPT DSSCs could be greatly tuned with molecular engineering on π-conjugated bridge,
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electron-donating and electron-accepting moieties [20-27]. In 2011, Yella et al.
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reported a D-π-A type porphyrin dye YD2-o-C8 with cosensitizer Y123 reaching a
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high PCE of 12.3% [3]. Since then, great efforts have been devoted to reengineer the
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structure of YD2-o-C8 for improving the light-harvesting capability. In 2014, Grätzel
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and co-workers synthesized dyes GY50 [21] and SM315 [12] by introducing
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2,1,3-benzothiadiazole (BTD) as a π bridge and simultaneously well-engineered
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donor based on YD2-o-C8, achieving a higher efficiency of 12.75% and a record
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efficiency of 13%, respectively, in a cobalt(II/III)-based ([Co(bpy)3]2+/3+) redox
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electrolyte without co-sensitizers.
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Even though porphyrin sensitizers exhibit a spectral feature covering the visible
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absorption region, 400-700 nm, it is still imperative to engineer the structures of
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D-π-A porphyrin sensitizers with enhanced NIR harvesting to improve the
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photovoltaic performance. However, it would be time-consuming and cost-expensive
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to synthesize porphyrins by conventional experimental approaches [13, 28, 29].
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Fortunately, theoretical calculation with low cost is becoming a powerful tool for the
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design of efficient dyes in DSSCs.
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In this paper, a series of porphyrin derivatives have been studied in theory
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systematically, based on experimentally synthesized dye SM315 with the record PCE
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by introducing better donors, π-bridges, and acceptor for more efficient porphyrin
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dyes. The models of all investigated dyes are shown in Figure 1. The photoelectrical
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properties including the ground-state geometries, frontier molecular orbitals (FMOs), 5
ACCEPTED MANUSCRIPT energy levels and absorption spectra and charge transfer (CT) characters of dyes were
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predicted using the density functional theory (DFT) and time dependent density
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functional theory (TDDFT) methods [30, 31]. In addition, some key parameters
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related to PCE were predicted, including exciton binding energy (EBE), light
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harvesting efficiency (LHE) curve, maximum short circuit current density ( J scmax ),
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injection driving energy (∆Ginj), driving force of regeneration (∆Greg), conduction
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band energy shift (∆ECB) and dipole moment (µnormal). We hope our work could offer
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theoretical guideline for experimentalists in the effective design of highly efficient
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porphyrin sensitizers to improve the PCE of DSSCs.
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Figure 1. Chemical structures of the studied Zn-porphyrin dyes. The hexyl and octyl groups are
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replaced by methyl groups marked with dashed and solid circles, respectively.
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2. Computational Details
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The ground-state geometries of the dye molecules were fully optimized at hybrid
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DFT levels by B3LYP function with LANL2DZ basis set, which has been proven to
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be relatively reliable for optimizing the geometries of porphyrin dyes [16, 32]. On the 6
ACCEPTED MANUSCRIPT basis of ground-state optimized geometries, the vibrational frequency calculations
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were performed at the same level of theory to confirm that the optimized geometries
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are local minima (no imaginary frequencies) on the potential energy surfaces. The 12
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lowest singlet-singlet excitations were calculated using the TD-DFT method in
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conjunction with the linear-response IEF-PCM model (integral equation formalism
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polarizable continuum model) in its non-equilibrium limit [33, 34] in solvent
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tetrahydrofuran (THF) phase without any further parameter.
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With the aim to select a reliable functional to evaluate the vertical excitation
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energies, different time-dependent density functionals, including TD-B3LYP [35],
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TD-CAM-B3LYP [16, 36], TD-PBE0 [32], TD-HSE0 [37, 38], TD-BHandHLYP [39],
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TD-M06 and TD-M062X [40] were used. To enhance the computing efficiency, the
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hexyl and octyl groups of the dyes were replaced by methyl groups, which has been
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proved to have negligible effect on the photovoltaic properties of the porphyrin dyes
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[32, 41]. The absorption spectra by different methods along with experimental values
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of SM315 are presented in Figure S1 and Table S1. The maximum absorption
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wavelengths and band shapes indicate that TD-CAM-B3LYP is the optimal functional
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in general to be implemented to simulate the excited states of subject dye[12].
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Furthermore, the 0-0 energy[78] of SM315 (Table S1) using TD-CAM-B3LYP also
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has been conducted to make sure the reliability of the calculation for optical
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properties[12]. Although we are aware that such comparison between theoretical 0-0
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energy and experimental data should be made with care, the 0-0 energy simulations
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with various TD-DFT methods would be time-consuming and beyond our scope here.
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the investigated dyes. Frontier molecular orbital energy levels were obtained at the
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TD-CAM-B3LYP/LANL2DZ/IEF-PCM level in THF. The oxidation potential
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energies were determined at the M06/6-311G(d,p) level in THF [41]. All the
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calculations of the studied dyes were performed with DFT and TDDFT methods using
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the Gaussian 09 package [46]. For the further exploration of intramolecular charge
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transfer (ICT) from donor to acceptor [5, 42], the electron density difference maps
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(EDDs) and two charge transfer parameters (qCT, DCT) [43, 44] from the ground state
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(S0) to the first excited state (S1) were also investigated by Multiwfn 3.4 code [45].
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To gain an insight into the coupling interactions between dyes and TiO2 surface, the
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photoelectrical properties of porphyrin dyes adsorbed on the (TiO2)38 cluster were
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investigated with DFT calculations using DMol3 program [47, 48] in Material Studio
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Version 7.0. The geometries of (TiO2)38 cluster and dye-(TiO2)38 complexes were
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optimized using the generalized gradient-corrected approximation (GGA) method [49]
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with Perdew-Burke-Ernzerhof (PBE) functional [50, 51] and double numerical
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polarization (DNP) basis set. The excitation energy of (TiO2)38 cluster is in good
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agreement with the experimental results of the TiO2 semiconductor, proven to be a
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reasonable model to mimic the effects of the semiconductor surface in previous works
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[52, 53]. All dyes were adsorbed on the TiO2 surface through bidentate bridging mode
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[54], which is one of the stable modes for carboxylic acid anchor on TiO2 surface [55,
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56]. Then, the electronic structures of dye-(TiO2)38 complexes were investigated
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through single point calculations at the CAM-B3LYP/SVP/IEF-PCM level [57] in
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THF using the Gaussian 09 package. Subsequently, the simulated total density of
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states (TDOS) of the (TiO2)38 cluster and partial density of states (PDOS) of TiO2 in
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the dye-(TiO2)38 complexes were obtained with GaussSum 3.0.1 [58].
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3. Results and Discussion
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3.1 Screening of π-Conjugated Bridge
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The π-conjugated bridge is a key part of the D-π-A structure in dye for high
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performance DSSC devices. To screen predominant π-bridge candidate of porphyrin
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derivatives, we simulated molecular geometries, electronic structures and the
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characteristics of absorption spectra of five screened dyes F101-F105 (Figure 1) by
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introducing different π-conjugated bridges B1-B5 based on experimentally synthesized
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dye SM315.
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The optimized structures and geometrical parameters of the investigated dyes are
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illustrated in Figure S2 and Table S2, respectively. The dihedral angles Φ1 between
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π-linkers and acceptors in the screened dyes and SM315 are all close to 0°. The
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dihedral angles Φ2 formed between BTD and π-linkers in dyes F101-F105 are
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predicted to be -0.08°, -0.76°, 0.01°, 0.01°and -0.02°, respectively, which also
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approximate to 0°. However, the dihedral angle Φ2 of SM315 is -25.63° for the steric
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repulsion between hydrogen atoms. Therefore, the introducing of π-linkers B1-B5
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effectively improves the coplanarity of the screened dyes, which might be beneficial
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to intramolecular charge transfer behaviors [59].
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density distributions of frontier molecular orbitals (FMOs, Figure 2) for the studied 9
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SM315 is mainly localized on the donor group to the porphyrin ring moiety and partly
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spreaded over BTD moiety, while the electron density of LUMO plentifully
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distributes on the acceptor group, π-bridge and BTD moiety, less electron density
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around the porphyrin core. Such distinct charge separated states would facilitate the
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efficient electron injection from dyes to the conduction band of semiconductor (TiO2),
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while the overlap on the porphyrin macrocycle and BTD moiety of FMOs is
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beneficial for ICT transition [60] in the absorption process.
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Figure 2. Frontier molecular orbitals of the studied dyes at the TD-CAM-B3LYP/ LANL2DZ/
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IEF-PCM level in THF as solvent.
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The energy levels and HOMO-LUMO band gaps of the investigated dyes were also
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performed (Figure 3). Clearly, the LUMO energy levels of all dyes are above the
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conduction band of TiO2 (-4.00 eV) and the HOMO energy levels are sufficiently
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lower than the oxidation potential of [Co(bpy)3]2+/3+ electrolyte (-5.00 eV) [61, 62],
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species in the electrolyte. The HOMO-LUMO band gaps of F101-F105 are smaller
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than that of SM315 (3.55 eV). The results confirm that the LUMO energy levels can
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be decreased via different π-bridges and thence band gaps could be tuned.
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Figure 3. Frontier molecular orbital energy levels obtained at the TD-CAM-B3LYP/ LANL2DZ/
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IEF- PCM level in THF as solvent.
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the UV-visible absorption spectra (Figure 4, Table 1) and charge transfer properties
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(Table 2) of the dyes were carried out. Apparently, the absorption spectra of the
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screened dyes show obviously red-shifted Q bands and similar Soret bands compared
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to SM315. The molar extinction coefficients corresponding to λmax of dyes
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F101-F105 are 6.6108 × 104, 6.4199 × 104, 5.0607 × 104, 6.1287 × 104, 5.6652 × 104
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M-1 cm-1, respectively, exhibiting an increment of 22.4%-59.9%, compared to SM315
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(4.1342 × 104 M-1 cm-1). From Table 1, the maximum absorption wavelength (λmax)
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of F101 has 52 nm redshift compared to SM315.
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Charge transfer process plays an important role in DSSCs. The electron density
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spatial distance DCT) [43] [44] for the dyes are shown in Table 2. With the 11
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the donor, while the increasing electron density (purple) primarily distributes on the
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acceptor as well as BTD. The results show that the screened dyes perform
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comparable abilities in intramolecular charge transfer from donor to acceptor versus
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SM315. Furthermore, the values of qCT and DCT for the screened dyes are larger than
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the figures for SM315 (Table 2). Among the screened dyes and SM315, F101 has the
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best charge transfer performance with 0.658 e for qCT and 4.853 Å for DCT.
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Figure 4. The stimulated UV-Visible absorption spectra of the investigated dyes in THF solution.
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3.2 Design of D−π−A Structure
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Four dyes FSQ101-FSQ104 (Figure 1) were designed by employing the screened
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acid) as anchoring group based on dye SM315. The optimized structures and
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geometrical parameters of dyes FSQ101-104 are shown in Figure S2 and Table S2.
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The dihedral angles Φ1 and Φ2 in the designed dyes are all close to 0°, which would
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facilitate the intramolecular electron transfer. [63, 64]. From the Figure 2, it’s obvious
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that the electron density of HOMO for the designed dyes is mainly localized on the
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donor group as well as π-bridge and the density of LUMO is centered on the accepter,
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which could benefit the electron injection from dyes to semiconductor. Conspicuously,
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the energy levels of the designed dyes (Figure 3) could match the conduction band of
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TiO2 (-4.00 eV) and the oxidation potential of [Co(bpy)3]2+/3+ electrolyte. And these
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dyes show remarkably narrower HOMO-LUMO band gaps, especially FSQ101 and
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FSQ102 with the minimal energy gaps 2.92, 2.97 eV, respectively.
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Figure 4 displays the absorption spectra of the designed dyes, where the Q bands
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are significantly broadened and redshifted and the Soret bands are slightly red shifted
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comparing with SM315. And the absorption spectra of the designed dyes are extended
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into NIR region. The λmax of these four dyes are predicted to be 773, 764, 756, 757 nm,
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sequentially, which all achieve great enhancements compared to SM315 (651 nm).
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The molar extinction coefficients corresponding to λmax of dyes FSQ101-FSQ104 are
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9.9435 × 104, 9.7580 × 104, 10.0741 × 104 and 9.7780 × 104 M-1 cm-1, respectively,
20
showing a remarkable increment of 136.0%-143.7%, compared to SM315 (4.1342 ×
21
104 M-1 cm-1). The EDDs and the values of qCT, DCT also evince that the designed
22
dyes gain greater charge transfer characteristics than the screened dyes and SM315.
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Particularly, FSQ101 owns the best performance with 0.719 e for qCT and 6.269 Å for
2
DCT. Obviously, the designed dyes with larger λmax, higher molar extinction coefficients,
4
higher oscillator strengths, significantly broader and red-shifted absorption spectra
5
toward NIR region, larger qCT (e) and DCT (Å) might be promising candidates of
6
porphyrin sensitizers in highly efficient DSSCs.
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Table 1. Calculated electronic transition data in termed of excitation energies (E/eV), band
9
wavelengths (λ/nm), oscillator Strengths (f), and electronic compositions for the dyes in THF using TD-CAM-B3LYP/LANL2DZ on the IEF-PCM model.a E(eV) 1.76(S0→S1) 3.16(S0→S9)
λ(nm) 703 393
f 1.5806 1.1076
F102
1.80(S0→S1)
688
1.5197
3.16(S0→S8)
F104
1.82(S0→S1)
392
0.9155
679
1.2013
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F103
F105
FSQ101
FSQ102
H→L(65%) H-2→L+3(38%) H-2→L+1(8%) H →L(67%) H-2→L+2(5%) H-2→L+2(50%) H-1→L+1(5%) H→L(66%) H-2→L+2(6%) H-1→L+2(45%) H→L+1(8%) H→L(67%) H-2→L+2(5%) H-2→L+2(36%) H-1→L+1(8%) H→ L(67%) H-2→L+2(6%) H-2→L+2(38%) H-1→L+1(9%) H→L(60%) H-3→L(5%) H-2→L+3(19%) H-3→L(13%) H→ L(57%)
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Dyes F101
3.19(S0→S8)
389
1.1700
1.81(S0→S1)
685
1.4463
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3.13(S0→S7)
396
1.7063
1.81(S0→S1)
684
1.3446
3.16(S0→S7)
392
1.2668
1.60(S0→S1)
773
2.4426
2.81(S0→S7)
441
1.0833
1.62(S0→S1)
764
2.3902
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Composition H→L+1(11%) H→L+3(9%) H→L+2(8%) H →L+1(10%)
H-1→L(10%) H-2→L+2(9%) H-1→L(6%) H-1→L(10%)
H→L+1(22%)
H-1→L+1(6%)
H→L+1(12%)
H-1→L(9%)
H-4→L(12%)
H-1→L+1(11%)
H→L+1(11%)
H-1→L(9%)
H→L+3(15%) H-1→L+3(6%) H→L+1(11%)
H-3→L+3(12%) H→L+1(5%) H-1→L(9%)
H-2→L+1(11%) H→L+2(5%) H→L+1(13%)
H→L+1(9%) H-4→L(5%) H-1→L(11%)
H→L+1(17%) H-1→L+2(12%) H→L+1 (13%)
H-1→L(17%) H-1→L+1(6%) H-1→L(12%)
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1.0409
FSQ104
1.64(S0→S1) 3.13(S0→S10) 1.64(S0→S1)
756 396 757
2.4606 0.9169 2.3918
SM315
3.07(S0→S8) 1.91(S0→S1)
404 651
1.1799 0.9497
3.14(S0→S6)
394
1.5582
FSQ103
a
H→L+1(15%) H→L+3(31%) H→L+1(13%)
H-1→L(9%) H-2→L+1(26%) H-1→L(10%)
H-1→L(32%) H→L+1(16%)
H→L+2(11%) H-2→L+2(9%)
H→L+1(32%)
H-4→L(11%)
Only orbital percentage >5% are reported; where H=HOMO and L=LUMO.
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H-1→L(31%)
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H-3→L(6%) H-2→L+3(41%) H-3→L(5%) H→ L(57%) H-2→L+2(35%) H→ L(58%) H-3→L(7%) H-2→L+3(42%) H→L(63%) H-1→L(7%) H-2→L+2(37%) H-1→L(6%)
Table 2. The EDDs and CT parameters for all dyes corresponding to the S0→S1 transition. qCT (e)
DCT(Å)
F101
0.658
4.853
F102
0.604
3.932
F103
0.637
EDDsa
qCT (e)
DCT(Å)
0.719
6.269
FSQ102
0.693
5.937
4.541
FSQ103
0.658
5.425
0.607
4.171
FSQ104
0.683
5.739
0.634
4.489
SM315
0.564
3.734
Dyes
FSQ101
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F105
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a
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The isosurface of electron density is 0.0002 a.u.
EDDsa
The blue and purple colors symbolizes an decrease and increase in electron density, respectively.
6 15
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3.3 Dye Adsorption on the (TiO2)38 cluster In order to simulate the performance of the DSSCs more vividly, we explored the
3
photoelectrical properties of porphyrin dye adsorbed on the (TiO2)38 cluster. Evidently,
4
the dyes take the bidentate chemisorption with two Ti-O bonds of 2.115-2.152 Å
5
(Table 3 and Figure S3) [65-67]. The electron density of HOMO is entirely
6
delocalized on the dyes while the density of LUMO is centered on the conductor
7
(Figure S4 and Figure 5). It indicates that the studied dyes have sufficient potentials to
8
efficiently inject electron into the conduction band of TiO2.
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To figure out the feasibility of electronic injection from dyes to TiO2 surface, the
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adsorption energy (Eads) was estimated from the formula Eads=Edye+TiO2 -Edye-ETiO2,
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where Edye, ETiO2, and Edye+TiO2 are the total energy of isolated dye, (TiO2)38 cluster,
12
and dye-(TiO2)38 complex, respectively [68]. The negative Eads indicates that the
13
molecule adsorption is exothermic and stable. The adsorption energies (Table 3) of
14
dyes F101-F105 and FSQ101-FSQ104 were predicted to be -16.4, -0.8, -16.2, -16.8,
15
-15.9, -17.2, -18.2, -21.5 and -17.1 kcal mol-1, respectively. The adsorption energies of
16
the screened and designed dyes except F102 are comparable or even larger than that
17
of SM315 (15.1 kcal mol-1), which performs stronger interactions between the dyes
18
and the TiO2 surface. The adsorption energy of F102 is only -0.8 kcal mol-1, due to a
19
larger geometric distortion between dye and TiO2 surface. The results indicate that the
20
designed dyes could potentially lead to faster electron transfer rates and good
21
photovoltaic performances [35, 69].
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Figure 5. HOMO and LUMO orbital isosurfaces of dyes FSQ101-FSQ104 and SM315 adsorbed
3
on (TiO2)38 nanoparticle at the level of CAM-B3LYP/SVP/IEF-PCM.
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Table 3. The bond length (Å), and adsorption energy (kcal mol-1) of dye-(TiO2)38 complexes
6
calculated by PBE/DNP in the DMol3 module.
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Dyes
Ti-O(Å)
Ti-O(Å)
Eads(kcal mol-1)
Dyes
Ti-O(Å)
Ti-O(Å)
Eads(kcal mol-1)
F101 F102 F103 F104 F105
2.152 2.143 2.141 2.137 2.144
2.130 2.125 2.125 2.119 2.126
-16.4 -0.8 -16.2 -16.8 -15.9
FSQ101 FSQ102 FSQ103 FSQ104 SM315
2.139 2.146 2.130 2.139 2.149
2.121 2.118 2.115 2.124 2.124
-17.2 -18.2 -21.5 -17.1 -15.1
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3.4 The efficiency of DSSCs As known to all, the overall efficiency (η) of DSSCs is determined by the 17
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short-circuit current density (Jsc), the open-circuit voltage (Voc), the fill factor (FF),
2
and the incident solar power (Pinc) under AM 1.5 irradiation (100 mW cm-2). And it
3
can be expressed as [2]
5
η = FF
J scVoc Pinc
(1)
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3.4.1 Short-circuit current density (Jsc)
According to eq(1), enhancing Jsc and Voc are essential to improve the η of DSSCs.
7
Correspondingly, Jsc is the photocurrent per unit area (mA cm-2) when the DSSC
8
under irradiation is short-circuited. It is related to the interaction between TiO2
9
semiconductor and dye as well as the absorption coefficient of the dye. The Jsc can be
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described by the following equation [70]
J sc = e ∫ IPCE(λ )I s (λ )d λ = e ∫ LHE(λ )Φ injηregηcoll I s (λ )d λ
(2)
where e is the elementary charge, IPCE(λ) is the incident photon-to-current
13
conversion efficiency at a fixed wavelength and Is(λ) is the corresponding photon flux
14
based on the AM 1.5G (global) solar radiation spectrum. And IPCE(λ) is the product
15
of the light-harvesting efficiency at a relevant wavelength LHE(λ), the electron
16
injection efficiency (Фinj), the regeneration efficiency (ηreg) and the charge collection
17
efficiency (ηcoll).
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According to the experimental investigation performed by Kim et al., the dye with
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a lower exciton binding energy (EBE) will have a higher maximum incident
20
photon-to-current conversion efficiency (IPCE) [71, 72]. The EBE can be viewed as
21
the difference between the electronic and optical band gap energies. And it is
22
evaluated as [73] 18
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EBE=ELUMO－EHOMO－E0-0
(3)
where the E0-0 is an electronic vertical transition energy corresponding to the
3
maximum absorption wavelength. From Table 4, the EBEs of designed dyes are lower
4
than the ones of screened dyes and SM315, which indicates that the designed dyes
5
could be more potential to lead to higher short circuit current densities in DSSCs.
8
harvesting efficiency LHE(λ) can be obtained as followed: [8]
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For the same DSSCs, ηcoll can be seen as a constant. Correspondingly, the light
LHE( λ ) =1−10−Γσ (λ)
(4)
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where Γ is the surface loading of sensitizers (mol cm-2) grafted onto semiconductor
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and σ is the absorption cross section in units of cm2 mol-1 obtained from the decadic
11
extinction coefficient (units of M-1cm-1) by multiplication with 1000 cm3 L-1. Here, Γ
12
is set to 8.35 × 10-7 mol cm-2, according to the experimental value of SM315 [12]. The
13
calculated LHE curves are plotted in Figure 6. The curves are further extended step by
14
step in the order: SM315 < F103< F105 < F104 < F102 < F101 < FSQ103 ≈ FSQ104
15
< FSQ102 < FSQ101. Compared to SM315, the curves of dyes FSQ101-FSQ104 are
16
significantly red-shifted and broadened. Hence the designed dyes are expected to have
17
higher light-harvesting abilities and match better with the solar radiation spectrum.
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Figure 6. The plot of the simulated LHE curves of the studied dyes.
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When Фinj, ηreg and ηcoll are assumed to be unity, the calculated value of Jsc would
5
be the theoretically maximum short circuit current density ( J scmax ), which could be
6
used to reflect the overall light harvesting abilities of the dyes [41]. As is shown in
7
Table 4, it is clear that the J scmax of the designed dyes are higher than those of the
8
screened dyes and SM315, implying that the designed dyes have better light
9
harvesting abilities than other dyes. The calculated J scmax of SM315 (35.69 mA cm-2)
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is higher than the experimental one, because Фinj, ηreg and ηcoll are assumed to be 1.
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According to eq(2), we know that the Фinj and ηreg, which are closely related to the
12
driving force of electron injection (∆Ginj) and regeneration (∆Greg), could influence
13
Jsc . Generally, the ∆Ginj and ∆Greg can be described by [74, 75]
14
∆Ginj = E dye* − ECB = E dye + E0−0 − ECB
(5)
15
∆Greg = Eredox − Edye
(6)
16
where Edye*is the oxidation potential energy of the excited dye, Edye is the ground state 20
ACCEPTED MANUSCRIPT oxidation potential energy of the dye, ECB is the conduction band energy of TiO2
2
(-4.00 eV) and Eredox is the oxidation potential of [Co(bpy)3]2+/3+ (-5.00 eV) [61, 62].
3
The ∆Ginj of all dyes (Table 3) are in the range of 0.31 eV-0.58 eV. Islam et al. have
4
demonstrated that when ∆Ginj is above 0.2 eV, Фinj will be close to the unit [76]. This
5
means that an efficient electron injection occurs from all the investigated dyes into the
6
conduction band of TiO2. Moreover, the ∆Greg of all dyes are in the similar rank of
7
0.22-0.33 eV, indicating an efficient regeneration for all dyes. In a word, the driving
8
forces of electron injection and regeneration of the designed and screened dyes are
9
comparable to those of SM315.
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3.4.2 Open circuit photovoltage Voc
15
Besides the Jsc, the overall power conversion efficiency is also influenced by the open circuit voltage (Voc), which could be expressed as [77]
Voc =
ECB + ∆ECB kbT nc Eredox + ln − q q q N CB
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(7)
where ECB is the conduction band energy of the semiconductor, ∆ECB is the shift of
17
the conduction band energy level, q is the unit charge, kbT is the thermal energy, nc is
18
the number of electrons in the conduction band, NCB is the accessible density of
19
conduction band state.
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The Voc of the dye-(TiO2)38 complex is largely affected by the conduction band
21
energy shift, which is defined as the difference of the energy-axis intercept of the line
22
that fit the low energy contour of the partial density of states (PDOS) of TiO2 in the 21
ACCEPTED MANUSCRIPT complex and that of the total density of states (TDOS) of the TiO2 cluster alone
2
(Figure 7 and Figure S5). All the simulated values are listed in Table 4. The calculated
3
∆ECB of dyes are in the narrow range of 0.145 eV to 0.157 eV. The screened and
4
designed dyes own higher values of ∆ECB than SM315. Especially, the conduction
5
band energy shifts of FSQ101-TiO2 and FSQ104-TiO2 complexes are quite larger than
6
those of other dye-(TiO2)38 complexes.
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Figure 7. Total and partial density of states (DOS) of TiO2 cluster (black) and FSQ101-TiO2
9
complex (red). The intercepts of the dashed lines with the energy axis correspond to the calculated
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CB edges.
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Table 4. Calculated electronic properties of the isolated dyes and dye-(TiO2)38 complexes. Dyes F101 F102 F103 F104
J scmax -2
(mA cm ) 45.03 44.11 42.00 43.71
EBE (eV)
Edye (eV)
Edye* (eV)
Ginject (eV)
Greg (eV)
∆ECB (eV)
1.51 1.59 1.56 1.58
-5.32 -5.29 -5.33 -5.31
-3.56 -3.49 -3.51 -3.50
0.44 0.51 0.49 0.50
0.32 0.29 0.33 0.31
0.148 0.151 0.147 0.149
22
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1.56 1.32 1.35 1.40 1.38 1.64
-5.32 -5.23 -5.22 -5.33 -5.28 -5.33
-3.51 -3.63 -3.60 -3.69 -3.64 -3.42
0.49 0.37 0.40 0.31 0.36 0.58
0.148 0.153 0.145 0.150 0.157 0.147
Data in parenthesis is the experimental value from Ref [12].
2 3
0.32 0.23 0.22 0.33 0.28 0.33
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43.27 52.14 52.01 51.95 51.96 35.69(18.1)a
4. Conclusions
We first screened five dyes F101-F105 with different π-conjugated bridges B1-B5
5
based on experimentally excellent dye SM315. The results indicate that π-linker B1 is
6
the
7
FSQ101-FSQ104 with B1 as π-bridge, four strong electron-donating moieties D1-D4
8
as donor groups and cyanoacrylic acid as anchoring group. Four designed dyes
9
FSQ101-FSQ104 exhibit obviously smaller energy gaps, higher molar extinction
10
coefficients, dramatically broader and red-shifted UV-visible absorption spectra
11
covering the entire visible range up to NIR region. Importantly, the designed dyes also
12
show lower EBEs, larger ∆ECB, remarkably better light-harvesting abilities with
13
broader LHE curves and larger J scmax compared to dye SM315, which could facilitate
14
the improvements of Jsc and Voc and then benefit the increments of the overall power
15
conversion efficiencies in DSSCs. In particular, FSQ101 is the most promising
16
sensitizer candidate for the highly efficient DSSCs. It is expected that this theoretical
17
study will provide valuable strategies for the development of highly efficient D-π-A
18
type porphyrins in future DSSCs.
promising
π-conjugated
bridge.
Then
we
designed
four
dyes
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Corresponding Author *E-mail: [email protected]; [email protected]
Notes The authors declare no competing financial interest.
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Acknowledgements
This study was supported by the National Key Research and Development Program
7
of China (2016YFB0700504), Natural Science Foundation of Shanghai, China
8
(16ZR1411500), Shanghai Municipal Education Commission (Peak Discipline
9
Construction Program) and the High Performance Computing Center of Shanghai
10
University.
11
Appendix A. Supplementary data
Supplementary data related to this article can be found at
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Supporting Information Theoretical Screening and Design of SM315-Based Porphyrin Dyes for Highly Efficient Dye-Sensitized Solar Cells with Near-IR Light Harvesting
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Yan Fu, Yongxin Xu, Tian Lu, Minjie Li*, Zhen Wei, Huan Liu, Wencong Lu*
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Department of Chemistry, College of Science, Shanghai University, Shanghai 200444,
Email:[email protected]; [email protected]
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Tel:+86-21-66133513
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Index
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Table S1…………………………………………………………………………………………. S1 Figure S1………………………………………………………………………………………… S2 Figure S2…………………………………………………………………………………………S3 Table S2.………………………………………………………………………………………….S5 Figure S3.…………………………………………………………………………………………S6 Figure S4.…………………………………………………………………………………………S7 Figure S5.…………………………………………………………………………………………S9 The Cartesian Coordinates of molecules discussed in the text……………………………...…...S10 The Cartesian Coordinates of dyes ……………………………………………………………...S10 F101.……………………………………………………………………………………………..S10 F102.……………………………………………………………………………………………..S14 F103.……………………………………………………………………………………………..S19 F104.……………………………………………………………………………………………..S23 F105.……………………………………………………………………………………………..S27 FSQ101.………………………………………………………………………………………….S31 FSQ102.………………………………………………………………………………………….S35 FSQ103.………………………………………………………………………………………….S39 FSQ104.………………………………………………………………………………………….S44 SM315.…………………………………………………………………………………………...S48 The Cartesian Coordinates of dye-TiO2 complexes……………………………………………...S52 F101-TiO2.……………………………………………………………………………………….S52 F102-TiO2.……………………………………………………………………………………….S59 F103-TiO2.……………………………………………………………………………………….S66 F104-TiO2.……………………………………………………………………………………….S73 F105-TiO2.……………………………………………………………………………………….S80 FSQ101-TiO2.……………………………………………………………………………...…….S87 FSQ102-TiO2.……………………………………………………………………………...…….S93 FSQ103-TiO2.……………………………………………………………………………...…...S100 FSQ104-TiO2.……………………………………………………………………………...…...S107 SM315-TiO2.……………………………………………………………………………...…….S114 The Cartesian Coordinates of TiO2 cluster……………………………………………………..S121
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λmax(nm) 915 651 819 1001 644 816 639 668a
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f 0.4966 0.9497 0.6739 0.3327 1.0736 0.7349 1.0197 ----
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so given for comparison.
a
E0-0(eV) ---1.75b ---------------1.79a
The data from reference [12] in manuscript. To reduce the cost of time and computation, only the E0-0 of SM315 using TD-CAM-B3LYP was calculated.
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(a) The band shapes of SM315 with different computational methods
(b) The screenshot of experimental spectra from the original article of SM315 Figure S1 The theoretical and experimental absorption spectra of SM315.
S2
F101
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F102
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F104
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F103
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Figure S2. The optimized geometries for the studied dyes at the B3LYP/LANL2DZ
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Φ1(°) Φ2(°) 0.01 -0.08 -0.44 -0.76 -0.01 0.01 0.02 0.01 -0.02 -0.02 0.00 -0.04 -0.03 0.53 -0.03 -0.67 0.03 -0.10 -0.31 -25.63
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angles. (Φ1, Φ2 represent the dihedral angles)
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Figure S3. The optimized structure of dye-(TiO2)38 adsorption complexes calculated at
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the GGA/PBE/DNP level in DMol3 Program.
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Figure S4. Interacting orbital isosurfaces of dyes F101-F105 adsorbed on (TiO2)38
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nanoparticle.
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Figure S5. Total and partial density of states (DOS) of TiO2 cluster (black) and
dye-TiO2 complex (red). The inercepts of the dashed lines with the energy axis
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correspond to the calculated CB edges.
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The Cartesian Coordinates of molecules discussed in the text The Cartesian Coordinates of dyes
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-0.01029900 -0.90719500 0.84226400 -1.07522900 -1.81155400 0.91059600 1.80037500 -0.13562000 -2.05741700 -2.51450500 -1.88766900 1.88185700 2.43570100 1.95625900 0.82226700 -1.20126200 -2.55358500 -3.27422600 2.28797100 3.20987700 1.78768900 0.63305400 -1.11249300 -2.14745800 -3.60142500 3.34384900 2.20235700 1.49342700 -0.26476200 -2.02049200 -2.65661400 -3.23712600 -4.97772100 4.71510200 2.99374200 2.93699900 1.54079900 -0.30465900 -2.14562600 -3.39814000
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0.00583300 -0.92726200 0.87732200 -1.15754400 -1.78239700 0.98207300 1.79015300 -0.15357200 -2.13647100 -2.52998300 -1.81003300 1.93726100 2.44532300 1.91261200 0.83248500 -1.27393600 -2.66476000 -3.27268200 2.34980100 3.19551000 1.83840300 0.63378100 -1.19666100 -2.26380400 -3.73828000 3.41634500 2.27210900 1.53360600 -0.31071100 -2.15979900 -2.81551000 -5.10125100 -3.41473100 3.07850500 4.78603900 3.03979700 1.58471900 -0.36011000 -2.30594600 -3.59815400
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-4.68222500 -4.11099100 -3.96557300 -2.74742200 -4.86300400 -2.57776800 -4.56855500 -1.20251600 -2.62197100 -3.94577800 -5.93974500 -2.29260200 -3.53832900 -5.62990900 0.34056400 0.17161300 -1.40580700 -4.14218900 -0.99985500 -3.61038400 0.21035200 1.69714500 1.55057700 -0.12033200 -1.49976500 -0.91712600 1.53795500 2.45603600 2.27874800 2.15531300 1.12669200 -1.59497100 -1.50288600 -0.84985000 -0.90241800 1.73403800 3.53559900 3.69731900 3.21848600 1.19841400
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-4.21288700 -1.86557000 -5.96873700 -5.26527900 5.71461700 4.98879500 3.97818400 1.62617400 -5.57014300 -3.92833100 -1.38944200 -7.02319200 -6.65607000 5.32993900 6.76508400 6.37189000 3.70476600 1.16704400 -6.32712200 -1.73274300 -1.71307800 -0.30071900 -7.20166900 -7.16177900 -6.61566000 6.09346900 6.96397700 6.32026300 6.83562800 1.45610300 1.55667200 0.07905300 -0.29494300 -0.22574900 0.66969900 -0.98261000 0.75849500 1.46337900 -0.89381900 -1.66493900 -0.05388400 1.62898500 2.36073900 -1.52481800
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-6.11833100 -5.34752500 -4.41707000 -2.05370300 4.07337200 1.71161800 5.79596800 5.04671500 -5.75992200 -7.16216600 -6.71766300 -4.16411800 -1.62218200 5.42337000 3.80943200 1.26476100 6.84522400 6.42852800 -6.53707800 -7.34014600 -7.16263700 -6.64240000 -2.03894100 -1.90407400 -0.53453000 6.19500300 1.62930300 0.17475800 1.58988700 6.93767700 6.98386800 6.36623100 -0.35569700 -0.28792000 0.66182400 -1.09578000 0.75160900 1.50796800 -1.00634900 -1.81957500 -0.11520300 1.67612500 2.45878400 -1.67924200
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-1.69109900 -1.58444000 -1.59785800 -1.40914000 -0.76750100 -0.87313100 -0.82114800 -0.97124100 -1.69102500 -1.76376100 -1.71427200 -1.60092700 -1.40744500 -0.75431200 -0.71558900 -0.78457500 -0.80933500 -0.96154300 -1.76477000 -0.87640600 -2.66518300 -1.69496000 -0.54960200 -2.34125700 -1.32442300 -0.69123100 -1.63538500 -0.81205300 0.15686200 -0.03180100 -1.82582700 -1.02400900 4.92891100 6.33604900 6.97799000 7.19397300 8.45097100 6.29958800 8.60887900 6.75863900 9.29151500 8.90164400 7.49111600 9.18493000
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0.03921900 0.65826500 -0.53080700 1.71505500 0.21170800 -1.65571000 0.02262700 2.30322700 2.06856300 0.81337700 -0.60958800 -2.19783700 -2.10928200 -0.53673000 0.89647800 1.87919400 3.09500500 0.44374300 -1.65757800 -3.07954900 -0.09342500 2.57660600 -2.23007000 1.90783300 3.97093000 -2.69126400 -2.35860800 2.61039500 0.52281800 4.69768200 4.51462000 -3.25832000 -2.57987500 -2.92006500 -1.91698800 4.00354800 2.11472800 -0.22924600 5.77153800 -3.36994800 -3.58626200 -3.02782200 -2.13566700 4.59368600
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0.07544000 -0.99342200 1.21654900 -1.72944400 -1.37344600 1.86441200 1.74666900 -2.79895200 -1.47017700 -2.43778600 -0.83715700 3.00390000 1.47031300 2.87682100 1.27908800 -3.17751700 -3.36073000 -2.71090400 3.54139000 3.46183800 3.25756800 -4.27643900 4.78447100 -5.21713300 -4.43651800 5.81623500 5.00591700 -6.24395300 -5.07316700 -5.45802900 -3.71970700 7.01141900 5.69151500 6.18934700 3.97913700 -6.36551100 -6.96624000 -6.07781600 -5.52110900 7.19110400 7.77077600 6.36844900 4.09491900 -7.42387100
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-6.12696300 -6.84816400 -6.77584000 -6.26499900 -8.13738500 -6.21655200 -7.96646000 -6.95447800 -5.27179100 -8.82077600 -8.60288700 -6.82690700 -5.31228900 -8.57641500 -8.41011200 -8.25125400 -6.46445700 -9.80232900 -8.02032100 -6.38451800 -9.48939600 -8.97743000 -8.60920500 -9.82016900 -8.84238300 -7.76637500 -10.01517800 -10.46958600 -9.94638600 -9.48199900 -8.23279000 -8.24697200 -6.69256900 -10.51883900 -10.85501600 -10.30064500 -11.10758900 -10.68435200 -9.34311900 -9.63647400 -7.54535200 -11.58224700 -12.28983900 -10.99875300
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N C C C C C C C H C H C H C H C H H C H H C C C C C C C O C H C H C O C H C H C H H C O
S12
ACCEPTED MANUSCRIPT
RI PT
-0.09006700 0.05844200 -1.27481000 -3.90598000 -1.57967200 -3.20426700 -1.75872700 6.03120900 -4.39321400 6.58420300 6.25990400 6.31710700 -4.76411800 -3.58482400 -5.21110600 0.01056400 -1.04232700 0.78721100 -0.35987300 0.57122800 1.46828400 -0.49068000 1.10522200 0.36137100 -1.41386100 2.52333300 0.88045600 0.31517700 -0.58379500 0.89294500 -0.86510500 -0.34288400 -1.81412400 -1.98806300
SC
-7.07672100 -6.09529500 -5.77656400 8.32529200 4.94341700 4.20281100 3.16119000 -7.61747500 9.40738700 -6.74476300 -8.48982200 -7.81465200 10.16749000 9.82832900 9.06761700 -0.05077200 -1.17640000 0.77556400 -0.45170900 0.54233900 1.50244300 -0.59425500 1.10922100 0.31384700 -1.58180900 0.97435200 2.51565200 0.26174400 -0.69853700 0.87693300 -1.00183700 -0.44708400 -2.01472800 -2.20266800
EP
TE D
M AN U
-10.24863600 -11.74481800 -10.59189300 -10.25446400 -12.71223300 -12.52091000 -12.71238200 -10.87430000 -9.41143300 -11.24888600 -11.48997900 -9.83165400 -10.10211000 -8.79735300 -8.76076500 10.73973600 11.75831000 11.55901800 13.22758100 12.93551400 11.13689700 14.66013000 14.24165000 15.29978700 15.80530900 14.35414000 14.35714800 16.70844700 17.17074500 17.38799800 18.56569800 19.55250300 18.70062100 19.64978600
AC C
H H H O H H H C C H H H H H H C S C C C H C C C S F F C C H C O O H
S13
ACCEPTED MANUSCRIPT F102
RI PT
0.01298200 -0.87790300 0.80800700 -1.09323300 -1.72479600 0.81704300 1.75926600 -0.24777400 -2.04880800 -2.44038300 -1.75694200 1.74492700 2.33117400 1.95313800 0.61550800 -1.33024500 -2.57485800 -3.16764400 2.08570600 3.08190700 1.55344500 0.37938000 -1.29761100 -2.23143200 -3.58539300 3.10645500 1.90224500 1.18107000 -0.50927600 -2.19603700 -2.77017600 -3.17736300 -4.97036600 4.48320100 2.71854400 2.60431400 1.18514900 -0.60237900 -2.35666600 -3.48718200 -4.11846600 -1.79993600
SC
0.05471300 -0.92504300 0.92176200 -1.21511800 -1.77527900 0.97316200 1.88778700 -0.24713300 -2.22746100 -2.57964300 -1.76089100 1.94578300 2.52034400 2.05803000 0.70481600 -1.45434100 -2.81931500 -3.33623600 2.31723600 3.29732300 1.74241900 0.44416800 -1.43057400 -2.45943400 -3.91786300 3.40792900 2.13302100 1.33684400 -0.54975700 -2.44592400 -3.07797800 -5.26392000 -3.63487600 3.10397100 4.76631100 2.91331700 1.34409900 -0.65723600 -2.64014700 -3.88630300 -6.30337000 -5.47127500
TE D
M AN U
-5.96954300 -5.47254400 -5.18542300 -4.12730100 -6.29429400 -3.79318000 -5.71258200 -2.50733900 -4.08059600 -5.43706900 -7.37352100 -3.43081000 -4.63240100 -6.76112600 -0.88924700 -1.22307800 -2.90805400 -5.69398200 -2.10808700 -4.64319800 -0.93976900 0.45042600 0.16126600 -1.59158700 -3.08563300 -1.94019800 0.41971500 1.27840500 0.95731800 0.68974900 -0.38909600 -3.23103000 -3.11763300 -1.83233400 -1.88449600 0.67607500 2.36021200 2.37221400 1.74043600 -0.37862600 -3.40385400 -3.18789400
EP
AC C
C C C N C N C Zn C C H C C H N N C H C H C C C C C C C C C C C C C C C H H C H H C O
S14
ACCEPTED MANUSCRIPT
RI PT
-5.92721700 -5.30231300 5.45097700 4.79595600 3.67083900 1.34803100 -5.48540000 -3.80000200 -1.27951900 -6.98829100 -6.70505000 5.02889000 6.50559400 6.18642000 3.36785900 0.85109100 -6.21580800 -1.62822800 -1.56185300 -0.19453900 -7.26159400 -7.17538800 -6.70059900 5.76771200 6.80022100 6.16670900 6.60456700 1.08923300 1.25869400 -0.23150100 -0.63555400 -0.60887700 0.25338300 -1.37496500 0.30362200 1.05042400 -1.32535500 -2.03513900 -0.51704200 1.14919800 1.90337300 -1.96168900 0.12076000 0.80423200
SC
-4.65999200 -2.28861800 4.12031000 1.74698200 5.79748400 4.99441700 -5.98498300 -7.33402300 -6.81984800 -4.43775000 -1.89897300 5.45811800 3.88190500 1.33382500 6.83778400 6.36206900 -6.77962300 -7.48909300 -7.23080100 -6.71444000 -2.37086800 -2.15216500 -0.81559100 6.24633400 1.74985200 0.24497400 1.63073400 6.83950300 6.96310100 6.27423600 -0.69748300 -0.67623100 0.26424600 -1.52172500 0.30438400 1.14452600 -1.47998300 -2.23999600 -0.60294100 1.22528600 2.06675700 -2.17937000 0.18044500 -0.84185800
TE D
M AN U
-3.28916000 -2.97144600 -1.67059000 -1.90009900 -1.72388600 -1.99723500 -3.43043800 -3.51405700 -3.36361800 -3.31364200 -2.99140900 -1.61859200 -1.58806600 -1.77578400 -1.68131800 -1.94992800 -3.56291000 -2.56488400 -4.34264200 -3.30789300 -2.16986800 -3.95161800 -2.85795000 -1.49476300 -2.58673900 -1.85055000 -0.80406700 -0.98934400 -2.77451300 -2.05869800 3.60201600 5.01439100 5.71155400 5.82371700 7.18992000 5.08175600 7.24457000 5.34659900 7.98045900 7.69277600 6.32810500 7.78123100 -7.40808100 -8.13845500
EP
AC C
C O C O C O C H C H C C H C H C H H H H H H H H H H H H H H C C C C C N C H C N S H N C
S15
ACCEPTED MANUSCRIPT
RI PT
-0.46666900 1.86266100 0.41993800 -1.62883400 0.10469600 2.51194900 2.16855800 1.08191900 -0.40121900 -2.18998800 -2.09604500 -0.47350900 1.00713300 2.14934400 3.30298600 0.75839700 -1.63277900 -3.09945300 -0.01549900 2.90800300 -2.23063100 2.29983700 4.30120500 -2.75430300 -2.32527300 3.05717300 0.91613900 5.08242700 4.79954000 -3.35054300 -2.67058300 -2.91433300 -1.82221200 4.44674400 2.60719000 0.22349200 6.15233200 -3.42707000 -3.72714900 -2.99680000 -2.00652800 5.09463100 0.37899700 0.54938900
SC
1.32088500 -1.56116100 -1.19573800 1.91624100 1.90398200 -2.58888800 -1.32257000 -2.21840900 -0.67271600 3.05437800 1.48240300 3.03235100 1.47906600 -2.94085900 -3.14014000 -2.47274300 3.64320000 3.47016700 3.45344600 -3.99579800 4.88175700 -4.93450800 -4.11531400 5.87284200 5.13723700 -5.92179400 -4.83058700 -5.09639200 -3.39847100 7.05962000 5.72256100 6.31326500 4.15013700 -6.00385800 -6.64250600 -5.83896500 -5.12957300 7.27343100 7.78691300 6.51738500 4.29544500 -7.02526600 -6.84385300 -5.82051500
EP
TE D
M AN U
-8.04095800 -7.53745900 -9.45501700 -7.49910500 -9.19811500 -8.23557500 -6.52351100 -10.14623900 -9.93555500 -8.09439800 -6.62038700 -9.79367400 -9.62713100 -9.55815900 -7.73246800 -11.14895200 -9.25531800 -7.66673900 -10.68138000 -10.28809800 -9.82818700 -11.17762400 -10.10761100 -8.97309900 -11.23105900 -11.82685200 -11.34977400 -10.74662200 -9.46042200 -9.43924200 -7.90004300 -11.72039800 -12.08401400 -11.61135400 -12.49961000 -12.13887500 -10.57143700 -10.82619900 -8.72815000 -12.78156600 -13.52087100 -12.31381000 -11.72283400 -13.18822900
AC C
C C C C C C H C H C H C H C H H C H H C C C C C C C O C H C H C O C H C H C H H C O H H
S16
ACCEPTED MANUSCRIPT
RI PT
-0.83382700 -3.98567800 -1.47075600 -3.07184400 -1.58475200 6.53225900 -4.54023100 7.07013400 6.80985600 6.78783100 -4.91688600 -3.76871200 -5.36551500 -0.49112100 0.24051000 -1.53104100 0.02406700 0.90800100 -0.89292200 0.62102900 -1.16912800 -0.48744200 0.13447700 2.47763000 -2.24782600 -0.81815800 0.96888800 -1.08510500 3.16466000 3.20968200 -1.73796200 -0.41215700 0.59774400 1.91491700 -1.45782300 -1.74803300 4.53710700 2.63200000 4.58317300 2.71050200 -2.25069300 -0.61737500 1.25175500 -2.39702500
SC
-5.57289600 8.40445800 5.17391400 4.37128200 3.38706300 -7.17719400 9.44308700 -6.27951700 -8.02777800 -7.38920000 10.20874500 9.87565600 9.05510100 -0.59287300 0.21731700 -1.77308500 -0.04618000 0.97527200 -1.08076700 0.60440400 -1.41683000 -0.66110500 2.38849400 0.35257200 -2.65897000 -1.06526400 3.46402800 2.69264000 1.02538800 -0.54697600 -2.10978100 -0.63002500 4.79794600 3.26444400 4.02643000 1.88930000 0.80777400 1.72676700 -0.76544000 -1.07714600 -2.71698500 5.08249400 5.60854600 4.23827000
EP
TE D
M AN U
-12.07729500 -11.43045600 -13.90664700 -13.77857900 -13.95612000 -12.14252800 -10.57465100 -12.47814800 -12.76851400 -11.09489900 -11.25607600 -9.92234900 -9.96130600 9.43336300 10.30510400 10.38347600 11.68722800 9.91562300 11.90776900 13.37239400 13.28539100 14.25783000 13.76221300 13.62256500 13.98742300 15.57862800 13.36683600 14.41529400 14.66352600 12.80895300 15.64160000 16.48553200 13.61556600 12.86652300 14.66882600 14.72957100 14.88424200 15.30324400 13.02600000 12.00052400 16.85932600 14.26840100 13.30246800 15.17461300
AC C
H O H H H C C H H H H H H C C S C H C Si C C C C S C C C C C C H C H C H C H C H C C H H
S17
ACCEPTED MANUSCRIPT -0.08901800 1.33383800 -1.45811000 -2.38787600 -3.74870600 6.11338400 -0.25784600 -4.13791600
5.25006300 5.04547200 5.12765500 -1.94923900 -3.15427400 -0.90498000 6.31126600 -3.48014800
RI PT
14.06538600 15.68904100 12.38838200 18.02532600 16.59930300 14.46275700 14.23448600 17.44134700
AC C
EP
TE D
M AN U
SC
C H H O O H H H
S18
ACCEPTED MANUSCRIPT F103
RI PT
0.00143000 -0.92127600 0.88088000 -1.09526400 -1.85004100 0.95606100 1.86365800 -0.12294100 -2.10560300 -2.57406600 -1.92684500 1.95595700 2.52090900 2.02008700 0.86746300 -1.22125200 -2.61659700 -3.35504600 2.37729800 3.31675200 1.86393300 0.67387900 -1.12913800 -2.19777600 -3.69515900 3.46450100 2.29468700 1.56418200 -0.25317200 -2.06680200 -2.72337800 -3.37004300 -5.06163000 4.82534700 3.15477100 3.05396100 1.61531000 -0.29393000 -2.19609300 -3.48911300 -4.37442800 -2.00616300
SC
0.01992500 -0.88789900 0.86342500 -1.11526200 -1.71593200 0.96129600 1.75008000 -0.14440100 -2.06539500 -2.44395300 -1.74001400 1.88653600 2.38257000 1.87138300 0.80777000 -1.23381600 -2.58021400 -3.16409400 2.28222400 3.10980900 1.78257200 0.61141700 -1.16108600 -2.19315600 -3.62285200 3.31676400 2.19909500 1.48100600 -0.30426200 -2.09600100 -2.73032700 -4.99582600 -3.26025400 2.93899000 4.69621200 2.94226400 1.52704900 -0.35493600 -2.23936700 -3.48935600 -5.98470600 -5.28141200
TE D
M AN U
-3.16874700 -2.59861100 -2.45149500 -1.23532700 -3.35153800 -1.06362700 -3.05416100 0.31043200 -1.11066500 -2.43508100 -4.42834400 -0.77776000 -2.02357000 -4.11561800 1.85410400 1.68325300 0.10475500 -2.63219600 0.51498100 -2.09527100 1.72499900 3.21085100 3.06266200 1.39072600 0.01032000 0.59868300 3.05304700 3.97047900 3.79131400 3.66651800 2.63737700 -0.08413100 0.00674300 0.66382100 0.61623100 3.24986600 5.05012600 5.21092400 4.72957200 2.70858800 -0.18017700 -0.07305700
EP
AC C
C C C N C N C Zn C C H C C H N N C H C H C C C C C C C C C C C C C C C H H C H H C O
S19
ACCEPTED MANUSCRIPT
RI PT
-6.08088900 -5.31026100 5.85369300 5.05899200 4.16842400 1.79547400 -5.72087000 -4.11998000 -1.56997000 -7.12763600 -6.68810000 5.50876000 6.89598800 6.42822000 3.92592300 1.37755800 -6.49978700 -1.93361800 -1.90397200 -0.47956200 -7.24380500 -7.20353600 -6.61643100 6.29468700 7.03050300 6.34426400 6.90199600 1.68294500 1.78234800 0.28811500 -0.28410300 -0.21420500 0.71661800 -1.00176100 0.80802200 1.54201400 -0.91016500 -1.71108900 -0.03845800 1.71445100 2.47542200 -1.56605300 0.04931900 0.64440900
SC
-4.23393000 -1.89146100 3.90404300 1.56468700 5.67682400 4.99725400 -5.58768900 -7.03631900 -6.66517000 -3.95075300 -1.42042900 5.26473200 3.60909700 1.07712200 6.73363100 6.39192700 -6.34290200 -7.27472500 -7.10357000 -6.62171200 -1.82164800 -1.68726200 -0.33439700 6.01355400 1.42375400 -0.01088200 1.38834800 6.89053500 6.93718800 6.36205300 -0.35335600 -0.29312700 0.61940700 -1.07344000 0.70106300 1.43567200 -0.99128700 -1.76928800 -0.13677200 1.59068400 2.34764900 -1.64031700 0.09352800 -0.98555100
TE D
M AN U
-0.08772100 0.09962000 0.74649100 0.63800700 0.69823400 0.54927000 -0.18028500 -0.25252000 -0.19736300 -0.09081200 0.10407200 0.76261800 0.79621200 0.72587900 0.71220400 0.56221600 -0.25368300 0.64144200 -1.14778300 -0.17531200 0.96283200 -0.82888100 0.18736600 0.82593300 -0.12529300 0.69851400 1.66704100 1.49248700 -0.30156500 0.50117500 6.44201300 7.85081600 8.49650400 8.70397100 9.97096600 7.81948100 10.12103800 8.26624000 10.80677500 10.42337300 9.01368800 10.69626900 -4.61381200 -5.33968400
EP
AC C
C O C O C O C H C H C C H C H C H H H H H H H H H H H H H H C C C C C N C H C N S H N C
S20
ACCEPTED MANUSCRIPT
RI PT
-0.49750800 1.68717300 0.18660100 -1.60401100 0.06208400 2.25174900 2.04837200 0.76431600 -0.62494100 -2.12247100 -2.06193900 -0.47366000 0.92271500 1.81656100 3.03335900 0.38633000 -1.57587500 -2.99108300 -0.02592500 2.48985100 -2.12192100 1.79972500 3.88151700 -2.55527300 -2.25157900 2.48008900 0.41705700 4.58620400 4.44110200 -3.09670200 -2.44198700 -2.78789000 -1.83723000 3.87152600 1.96826300 -0.35733000 5.65931100 -3.21051600 -3.40396000 -2.89639800 -2.05836000 4.43867100 -0.23398600 -0.07601200
SC
1.24883700 -1.74522000 -1.35261300 1.92168800 1.76923300 -2.82421200 -1.49641300 -2.42707600 -0.79826300 3.07504300 1.53622100 2.91382500 1.28277800 -3.18992900 -3.40347200 -2.68989000 3.60296700 3.55222900 3.28655800 -4.30004600 4.86088400 -5.22597100 -4.48640200 5.90045300 5.08983500 -6.26397900 -5.05583900 -5.51965700 -3.78133100 7.10998000 5.76979400 6.28749300 4.05597500 -6.41180400 -6.97543400 -6.04482500 -5.60301300 7.29653900 7.87451200 6.47231100 4.18186400 -7.47909900 -7.04712400 -6.06506700
EP
TE D
M AN U
-5.25702800 -4.76157200 -6.62879300 -4.69040600 -6.44917900 -5.45606800 -3.76848400 -7.31695800 -7.09021800 -5.29523400 -3.78468300 -7.05336800 -6.89828900 -6.75279300 -4.97007300 -8.29817900 -6.49004800 -4.84728200 -7.96749800 -7.48472600 -7.07266100 -8.32655300 -7.35653900 -6.22464500 -8.47735600 -8.98185500 -8.44569300 -8.00204900 -6.74762800 -6.69898100 -5.15175900 -8.97483400 -9.32243400 -8.81980200 -9.61928800 -9.18161100 -7.86819800 -8.08736100 -5.99360300 -10.03718800 -10.75596400 -9.52360800 -8.74892500 -10.24374600
AC C
C C C C C C H C H C H C H C H H C H H C C C C C C C O C H C H C O C H C H C H H C O H H
S21
ACCEPTED MANUSCRIPT
RI PT
-1.39668800 -3.72327100 -1.48531100 -3.12513000 -1.70355000 5.87279900 -4.18177300 6.44036600 6.08260800 6.15960600 -4.53960100 -3.36090700 -5.00331400 0.01976500 -1.05824900 0.82752400 -0.34057600 0.62395200 1.53796600 1.16205700 -0.74843900 -0.29002900 -1.74224500 -1.99445000
SC
-5.72476800 8.44484400 5.01948500 4.31401200 3.24163200 -7.69978500 9.53468800 -6.83607200 -8.57383900 -7.90633600 10.30508900 9.93560400 9.21089600 -0.08708500 -1.15306300 0.70362900 -0.45439700 0.49619100 1.40499700 1.02173400 -0.86236200 -0.41640000 -1.84022800 -2.09290100
M AN U
-9.08255500 -8.69935200 -11.17731700 -10.98290000 -11.18324400 -9.40624300 -7.85028300 -9.77993000 -10.02623700 -8.36565000 -8.53644900 -7.23934300 -7.19606300 12.26179700 13.27017100 13.07911500 14.76878800 14.47409300 12.66345800 15.25484900 16.10680300 17.17778500 16.08490500 17.00113500
AC C
EP
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H O H H H C C H H H H H H C S C C C H H C O O H
S22
ACCEPTED MANUSCRIPT F104
EP
TE D
M AN U
SC
RI PT
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AC C
C C C N C N C Zn C C H C C H N N C H C H C C C C C C C C C C C C C C C H H C H H C O
S23
ACCEPTED MANUSCRIPT
RI PT
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SC
-4.25976000 -1.90579400 4.02260900 1.67325400 5.77601000 5.06841000 -5.61141300 -7.04445900 -6.64559600 -3.98774200 -1.44939600 5.37960600 3.73990600 1.20236400 6.83025800 6.45848400 -6.37620700 -7.23970500 -7.10911500 -6.59019000 -1.83640900 -1.74331400 -0.36102200 6.13789100 1.53804100 0.11318600 1.53775800 6.98130000 6.98834700 6.41570700 -0.17600200 -0.08259100 0.85757800 -0.85446300 0.97387200 1.67070700 -0.73998700 -1.57014100 0.14273800 1.88604700 2.62287500 -1.38530400 0.03063900 -1.05722000
TE D
M AN U
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EP
AC C
C O C O C O C H C H C C H C H C H H H H H H H H H H H H H H C C C C C N C H C N S H N C
S24
ACCEPTED MANUSCRIPT
RI PT
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SC
1.16433000 -1.79483300 -1.45573000 1.83422700 1.66672200 -2.88258500 -1.52246400 -2.53861500 -0.91944400 2.96706500 1.46235100 2.79068300 1.18253500 -3.27954300 -3.44419300 -2.82527300 3.47657400 3.44195600 3.14983400 -4.39860300 4.71400400 -5.34686000 -4.57130800 5.76518300 4.91131700 -6.39231200 -5.19042600 -5.61177000 -3.84965600 6.95659200 5.65901500 6.09052400 3.86576700 -6.52587800 -7.12025400 -6.19926800 -5.68390500 7.11212300 7.73136800 6.25128100 3.95889300 -7.60262700 -7.19210000 -6.23793200
EP
TE D
M AN U
-6.36990000 -5.83838500 -7.69553300 -5.80347700 -7.57985200 -6.51691700 -4.85479300 -8.36807100 -8.15892600 -6.42616700 -4.88370200 -8.20143300 -8.02929200 -7.80068000 -6.02778900 -9.33909200 -7.63893500 -5.97726400 -9.12886200 -8.51685000 -8.24117900 -9.33348600 -8.39826300 -7.40997100 -9.64866400 -9.97434700 -9.44325500 -9.02942300 -7.80910700 -7.90288500 -6.33607100 -10.16453600 -10.47702100 -9.82238400 -10.59274700 -10.15360000 -8.90393700 -9.29335600 -7.20980000 -11.22912300 -11.91011100 -10.50992500 -9.70273600 -11.21741200
AC C
C C C C C C H C H C H C H C H H C H H C C C C C C C O C H C H C O C H C H C H H C O H H
S25
ACCEPTED MANUSCRIPT
RI PT
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SC
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EP
TE D
M AN U
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AC C
H O H H H C C H H H H H H C S C C C H C H C S C H C H C O O H
S26
ACCEPTED MANUSCRIPT F105
RI PT
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SC
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EP
TE D
M AN U
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AC C
C C C N C N C Zn C C H C C H N N C H C H C C C C C C C C C C C C C C C H H C H H C O
S27
ACCEPTED MANUSCRIPT
RI PT
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SC
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TE D
M AN U
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EP
AC C
C O C O C O C H C H C C H C H C H H H H H H H H H H H H H H C C C C C N C H C N S H N C
S28
ACCEPTED MANUSCRIPT
RI PT
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SC
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EP
TE D
M AN U
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AC C
C C C C C C H C H C H C H C H H C H H C C C C C C C O C H C H C O C H C H C H H C O H H
S29
ACCEPTED MANUSCRIPT
RI PT
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SC
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TE D
M AN U
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AC C
EP
H O H H H C C H H H H H H C C S H C C S C C H C O O H
S30
ACCEPTED MANUSCRIPT FSQ101
RI PT
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SC
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EP
TE D
M AN U
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AC C
C C C N C N C Zn C C H C C H N N C H C H C C C C C C C C C C C C C C C H H C H H C O
S31
ACCEPTED MANUSCRIPT
RI PT
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SC
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TE D
M AN U
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EP
AC C
C O C O C O C H C H C C H C H C H H H H H H H H H H H H H H C C C C C N C H C N S H C C
S32
ACCEPTED MANUSCRIPT
RI PT
0.12886000 0.13208300 0.16000900 0.14430600 0.13147200 0.17527500 0.18086200 0.15168800 0.17549000 0.24263400 0.19943200 0.38091000 -1.05736700 1.10951600 0.15632200 -0.75454600 1.37139900 -1.85668000 -1.61521200 -0.79344400 0.87979000 -0.63857400 -1.09326800 -0.38285300 -2.40788500 -2.58314200 0.82737800 1.48901200 -0.67380900 -1.25937400 0.06231900 1.39716200 -1.29933400 0.03712000 0.73507800 -0.96102300 0.32519400 -0.01281900 -0.03431900 -0.00499200 -0.03121900 -0.01526600 0.00766200 -0.04059900
SC
0.00408200 1.20152300 -1.24149100 1.18761900 2.15521900 -1.26227800 -2.16835300 -0.05683700 2.12397100 -2.45887100 -0.33762700 -1.80889800 -3.32916700 -3.08545800 0.59267500 -2.42566000 -1.98855500 -2.77821700 -3.28129500 -4.38092900 0.34910900 1.76416000 -1.74999800 -3.34248400 -1.87300400 -3.49988500 1.25743600 -0.54491700 2.66702300 1.94749700 2.44102600 1.04236400 3.55467500 3.43803400 4.26873100 3.87507100 2.96795100 -0.42021900 1.08003600 -1.58836700 0.02813800 -1.32503500 -2.56657500 0.16505000
EP
TE D
M AN U
-9.91827900 -10.68246200 -10.61471300 -12.08565100 -10.16102300 -12.00301400 -10.04665300 -12.75443600 -12.62972000 -12.93734800 -14.12824400 -14.36451700 -12.98970500 -12.69758200 -15.19748300 -15.22199100 -14.80183800 -14.19578600 -12.04769400 -13.16857100 -16.38976700 -15.13070100 -16.01411700 -15.70243100 -13.90838000 -14.58727100 -17.45967500 -16.48379600 -16.20425400 -14.25988400 -17.38869800 -18.36186700 -16.12493000 -18.53286900 -18.35282500 -18.66288400 -19.48055100 9.58355500 10.66028000 10.35913800 12.09067800 11.74352000 9.89712200 13.52249600
AC C
C C C C H C H C H C N C C H C C H C H H C C H H H H C H C H C H H C H H H C S C C C H C
S33
ACCEPTED MANUSCRIPT -0.01358100 -0.03066900 -0.06098000 -1.13092200 1.12144200 -0.03871700 -0.05538200 -0.03305700 -0.06649700 -0.08309100 -0.06112700 -0.09126300 -0.09262600 -0.08444800 -0.10782700 -0.10033700 -0.11288800
RI PT
-2.15467400 -1.10812100 1.47487700 -3.04197600 -3.01804700 -1.09185600 0.21020600 -1.97413000 0.50108700 1.70475500 -0.37777800 1.64154900 2.98364100 0.59501200 2.89712200 4.03657400 2.82369200
SC
13.01737300 14.11686800 14.71207600 13.09243900 13.10493800 15.51704700 16.05846100 16.14768300 17.44989900 18.13196200 18.09754500 19.61057600 17.49252500 20.28881600 20.19381200 16.95012600 21.17474700
AC C
EP
TE D
M AN U
C C S F F C C H C C H C C O O N H
S34
ACCEPTED MANUSCRIPT FSQ102
SC
RI PT
-0.13022100 -0.01960500 -1.22284700 -0.70490200 -1.60102800 -1.99442900 -1.94703300 -0.10485300 -2.67954500 -2.67158400 -1.04715700 -2.47288400 -3.00858700 -0.78041600 -1.67251700 0.88804000 -3.38486600 -2.06570100 -2.94211100 -3.66308300 -3.56553400 -0.32825200 0.75223600 0.80400000 1.16366400 2.06371500 1.23116200 0.36107400 2.04391200 2.86888300 0.80016100 2.42037800 2.08900000 1.16261100 0.93631400 -0.61567100 2.50522100 2.42007600 2.34480400 3.83324800 2.46174900 0.83078400 -0.00552000 -0.05099500 1.24592900 -0.31817100 -1.13635600 0.17022900 1.33948400 -0.31772600 -1.04652800 0.14143000 -2.08119800 0.37005400 0.20690000 -0.09256400 2.28650200 -0.51770700 3.37393700 3.13570900 -4.46412300 -2.64783700 2.31343100 -0.59572900 -2.13292200 0.35026400 3.84085700 4.43934900 3.00418200 5.14029000 4.40571400 4.36181200 -3.44163400 0.60781300 -3.43264500 1.52754300 -3.77208800 -0.23670000 -4.88548000 -3.98462000 -4.07769400 -4.71594000 -5.21975600 -4.00829200
EP
TE D
M AN U
13.07712400 13.70748700 13.27936000 14.76773100 13.87709700 12.47676800 15.38034000 15.11076100 14.93675200 13.52143300 16.19555000 13.85573200 13.38161500 15.11186300 14.12941200 12.42163200 15.87073000 15.48367700 15.38186900 13.73163800 16.83523800 11.65882900 11.03129700 10.84141500 9.63356900 9.44277600 11.33363100 8.81023000 9.14464600 16.21524200 15.61120200 11.88573500 8.58984700 15.76995300 15.63836400 14.82986800 9.17784000 9.77879000 9.79789400 15.22030600 15.36498100 14.17322600
AC C
N C C C C H C H C H H C C C C H C H C H H C C C C C H C H O O O O C H H C H H C H H
S35
ACCEPTED MANUSCRIPT
RI PT
-0.84729800 0.02002300 -1.73672500 -1.02105300 0.72991400 -0.10571600 -0.10935600 -0.10290400 -0.23835000 0.04085500 -0.25154600 -0.37970300 0.06631200 0.18065800 -0.08543100 -0.39705500 -0.47725300 -0.39822200 0.21700700 0.28840300 0.19396300 0.07843700 -0.23277600 -0.45695400 -0.59145200 0.28956400 0.40493200 0.22460400 0.06443400 -0.20347000 -0.38011300 -0.61408500 0.44866200 0.30141200 0.20360000 -0.06601300 -0.33412300 -0.44244700 0.51595700 -1.89632500 1.73162400 -0.68029300 0.41504200 0.22244800
SC
3.62508800 3.98192700 3.61195200 4.28389900 -4.11821800 0.31704000 0.39553400 0.40701800 1.66128300 -0.85131400 1.85455400 2.94007400 -1.05483100 -2.12396100 0.39280700 3.22467900 3.90388800 3.07307300 -2.42564100 -3.09346600 -2.24215800 -1.06640500 1.84320300 3.86661400 4.97056200 -3.07762700 -4.15887400 -2.44243400 -0.87839500 1.64269100 3.22088700 5.36175900 -4.57248600 -3.11966300 -2.16010900 0.38012100 2.91863800 3.88892400 6.21144800 5.95760100 -5.16652300 -5.42342400 -4.18628100 -2.29558500
TE D
M AN U
11.30857600 10.73575000 10.66259300 12.16137200 8.32983200 7.39218600 6.16582700 4.73986700 4.07833200 4.08872100 2.70285200 4.75050400 2.71439700 4.77661600 1.24566700 2.48899000 3.77062300 5.82248000 2.51432600 3.80392600 5.85143900 -0.21033400 -0.22376400 1.22886900 3.89934300 1.25953700 3.94105000 0.00672800 -1.58072000 -1.59209000 -0.01822900 1.22523600 1.26929400 -1.28028800 -2.26069500 -2.24305500 -2.27881600 -1.30930500 1.23022800 1.21681100 1.27522300 1.27052500 -1.41009300 -3.33379300
EP
AC C
C H H H H C C C C C N C N C Zn C C H C C H N N C H C H C C C C C C C C C C C C C C C H H
S36
ACCEPTED MANUSCRIPT
RI PT
-0.34045700 -0.55368400 0.37836800 1.74695300 -2.05493900 -2.96390300 1.89208600 2.79790400 -0.54095500 -1.91200700 -0.91035300 1.24782600 2.96967600 -3.04051700 -4.32478900 0.74850400 2.87829800 4.15944800 -1.40962600 -3.13365400 -1.02405100 3.04111700 3.03378800 3.78028800 -4.51485500 -4.52945400 -4.96505900 0.86358300 4.36316300 4.79850700 4.35210500 -3.19138400 -3.20996500 -3.94512100 4.79859900 -4.22785700 -0.05571500 -0.03943800 -0.01039600 0.13748200 -0.11631600 0.17243800 0.25078000 -0.08315000
SC
3.04430900 4.95460500 7.61743400 5.55773800 7.36140400 5.06154000 -6.57010000 -4.26894100 -6.82921500 -4.77106500 8.17425200 8.26532000 6.34880100 7.81330900 5.58004500 -7.38438400 -7.02068100 -4.78554600 -7.47817100 -5.56351000 9.25566200 6.97403600 6.98060500 5.61786500 6.17761500 6.18363200 4.69605200 -8.46566600 -5.38467500 -3.90068200 -5.38692100 -6.19253700 -6.19156100 -4.83354000 4.49839900 -5.72269700 0.35551400 0.26810100 0.08159800 -1.25573600 1.12580400 -1.47698800 -2.36205100 0.90847200
TE D
M AN U
-3.35189900 -1.44880200 1.22617700 1.23890700 1.21264200 1.21276700 1.28156800 1.27390000 1.27696300 1.26434800 1.21727500 1.22920100 1.24107400 1.20535200 1.20006500 1.28214200 1.28453000 1.26645600 1.27646200 1.25238900 1.21351800 0.34043300 2.13772900 1.24698300 0.29786500 2.09509600 1.19776900 1.28575300 2.16473900 1.26140000 0.36736400 0.35342100 2.15076300 1.24358500 16.56433500 15.87768100 -3.66055900 -4.88986500 -6.28542700 -6.83989500 -7.21568200 -8.30102200 -6.08583700 -8.61678400
EP
AC C
H H C O C O C O C O C H C H C C H C H C H H H H H H H H H H H H H H H H C C C C C C N C
S37
ACCEPTED MANUSCRIPT
RI PT
-0.22785600 0.05707200 0.31458000 0.40747300 -0.17255200 0.08585000 -0.07994400 0.22784800 0.05490600 0.20945600 0.33704100 0.05260300 0.31902800 0.20695500 -0.08930900 1.54144200 -0.69533700 0.21855900 0.07158300 0.32784200 0.05103000 -0.08292200 0.15985400 -0.06079000 -0.23859800 0.06784700 -0.20101200 -0.36694700 -0.18229400
SC
2.14082900 -0.35276600 -2.76606900 -3.73736600 1.78572100 -0.53514500 0.92540500 -1.71583200 -0.15751300 -1.49163600 -2.67476900 -0.06008400 -2.34950600 -1.33999500 1.20830500 -3.08754500 -3.35352700 -1.36153200 -0.08345600 -2.25440000 0.16788200 1.34462000 -0.72202100 1.24294700 2.63136200 0.18602300 2.47430100 3.69107500 2.37627800
TE D
M AN U
-6.84676000 -9.21764200 -8.66633700 -7.18750900 -9.25334700 -10.65422300 -11.77220100 -11.39690700 -13.17277700 -12.78810600 -10.90795900 -14.60803400 -14.03829600 -15.16652100 -15.83369400 -14.08759900 -14.10235100 -16.56671800 -17.14414000 -17.17247500 -18.54330000 -19.25833000 -19.16623100 -20.73483600 -18.65446800 -21.38405900 -21.35180500 -18.14121800 -22.33042800
AC C
EP
H C N S H C S C C C H C C C S F F C C H C C H C C O O N H
S38
ACCEPTED MANUSCRIPT FSQ103
RI PT
0.10955600 0.13245700 0.15831500 1.21925300 -0.87845800 1.41718200 2.26298700 -1.02957000 -1.94420200 0.21735200 2.56416100 3.09317900 2.33587700 -2.16756900 -2.73954900 -2.05362900 -0.98023400 1.46400300 3.13202000 3.97380900 -2.69410600 -3.62318300 -2.14015600 -0.79777100 1.32254300 2.61722600 4.38772100 -3.94889300 -2.68745900 -1.86368600 0.27279900 2.40953300 3.20584700 5.66013300 4.33016500 -3.88935400 -5.22220200 -3.58206800 -1.95905800 0.27666700 2.53661300 4.10471800
SC
0.02045800 0.02817000 0.04126800 0.75274000 -0.65619500 0.86485000 1.47917000 -0.73547700 -1.40115000 0.08296500 1.63774000 2.02078900 1.57363200 -1.50463400 -1.92081900 -1.52206000 -0.70061900 0.90581500 2.00539900 2.62700000 -1.84067000 -2.53264100 -1.46347000 -0.57213100 0.81513600 1.66206400 2.83097100 -2.66780200 -1.81278000 -1.26577900 0.13147500 1.52742700 2.04799700 2.21472200 4.24349800 -4.08001200 -2.05327400 -2.39801200 -1.32063700 0.14178500 1.61179100 2.63704300
TE D
M AN U
5.00715600 3.77696800 2.34860600 1.71685500 1.66529700 0.34649900 2.41965500 0.28630900 2.31415400 -1.14730800 0.16586000 1.46381200 3.49320000 0.04800300 1.31747500 3.38200500 -2.63979000 -2.58012400 -1.07658000 1.61885700 -1.22211900 1.42676200 -2.45841600 -4.00536400 -3.95352200 -2.34022100 -1.04201600 -1.24978100 -3.76200300 -4.71768400 -4.63555100 -4.60768300 -3.61378000 -1.02201900 -1.02686700 -1.27517600 -1.25299900 -3.91832100 -5.79384600 -6.05421300 -5.67730000 -3.72530000
EP
AC C
C C C C C N C N C Zn C C H C C H N N C H C H C C C C C C C C C C C C C C C H H C H H
S39
ACCEPTED MANUSCRIPT
RI PT
6.84689800 5.64134300 5.50546700 3.04478600 -5.06376800 -2.60301200 -6.40812200 -5.20506600 6.75181700 7.82061800 6.90332300 5.45690200 2.88143300 -6.31114100 -5.01376600 -2.43783700 -7.38262000 -6.46803700 7.66088100 7.51365300 7.47277700 6.62345200 3.34297500 3.30578600 1.80249600 -7.21955300 -2.89176700 -1.35855400 -2.86876200 -7.04059300 -7.07467600 -6.18951400 0.22081900 0.07803000 -1.04525000 0.96756300 -1.21924400 -1.98544300 0.79720800 1.82087700 -0.26183800 -2.30401800 -3.13586600 1.54349700
SC
2.98010500 0.82112200 5.02651700 4.78207500 -4.86451100 -4.61669300 -2.82010600 -0.65980700 4.38064300 2.50328200 0.09433200 6.10971000 6.22925100 -4.22034800 -5.94751800 -6.06341900 -2.34463700 0.06535500 4.97665200 0.33214700 0.30960500 -0.96050900 6.69465500 6.66497500 6.39313100 -4.81750000 -6.53544000 -6.22592700 -6.49340600 -0.14642700 -0.17738500 1.12048300 0.11350400 0.03167800 -0.69169200 0.61577300 -0.79062800 -1.30845000 0.51725500 1.16558600 -0.16292700 -1.49003100 -2.04448200 1.00642900
EP
TE D
M AN U
-0.98767800 -1.03896200 -0.99265500 -1.04793100 -1.30463500 -1.26808500 -1.28251600 -1.22545600 -0.97340600 -0.97209700 -1.01934700 -0.98121200 -1.02751600 -1.30823600 -1.32431600 -1.29966600 -1.28611500 -1.23661300 -0.94684100 -1.90142900 -0.10473700 -1.03898300 -1.90926400 -0.11257500 -1.04714900 -1.33143100 -0.41747500 -1.28964500 -2.21423700 -2.15004900 -0.35327400 -1.21321600 -7.28472000 -8.68421700 -9.26031100 -9.59657800 -10.72454200 -8.52458700 -11.00195600 -9.21133600 -11.62299300 -11.11086000 -9.64874200 -11.62365200
AC C
C O C O C O C O C H C H C C H C H C H H H H H H H H H H H H H H C C C C C N C H C N S H
S40
ACCEPTED MANUSCRIPT
RI PT
0.08096600 1.29922500 -1.16647900 1.26382500 2.57267200 -1.19021100 -2.41188000 0.02220900 2.49863200 3.74274000 2.60164600 -2.45326100 -2.39642900 -3.61039800 -0.00823600 3.70276400 2.46994200 4.69759700 -3.62888700 -2.46882200 -4.54332900 -0.54589200 0.50170200 4.62606400 -4.57413900 -0.42135400 -1.24028300 0.40818700 1.13889000 -0.98165700 0.12083500 -1.78126300 -1.36309400 0.94393800 -0.09054500 1.65489800 1.23747800 -1.67426100 -0.84577900 -2.30438000 1.57964900 0.83301600 2.13369400 -2.29992600
SC
0.01526900 0.12404700 -0.09661300 0.14736800 0.22283600 -0.12150400 -0.19515700 0.01357900 0.32548000 0.37194200 0.16791100 -0.30081200 -0.13909900 -0.34589000 0.01674200 0.43657300 0.36779000 0.44284600 -0.41203100 -0.34440300 -0.41700000 1.16099200 -1.12281500 0.57066400 -0.54745700 2.44608400 1.04085700 -2.41061700 -0.99543100 3.56554300 2.56868900 2.16860800 0.06341900 -3.52538600 -2.53873900 -2.11867200 -0.01597700 3.46051900 4.54369500 2.04725000 -3.41300600 -4.50572400 -1.99167600 4.66597700
TE D
M AN U
6.43289500 7.17431300 7.12359900 8.62216600 6.51755900 8.57165600 6.41510500 9.30277600 9.33891100 7.23985400 5.43390300 9.23711700 5.33126200 7.08873300 10.74536500 8.67037000 10.42134700 6.72486800 8.51964900 10.31978200 6.53506400 11.41853300 11.44704600 9.22816700 9.03905700 10.84411100 12.64646200 10.87268300 12.70498400 11.47536400 9.91138400 13.27719800 13.10293800 11.53294400 9.91672300 13.36400400 13.16294500 12.70564700 11.02003600 14.21883300 12.79295300 11.07551700 14.32822500 13.31826900
EP
AC C
C C C C C C C C C C H C H C N C H H C H H C C H H C C C C C H C H C H C H C H H C H H C
S41
ACCEPTED MANUSCRIPT
RI PT
-2.90231800 -2.32133600 -3.49893400 -2.92891000 -2.91019000 -3.49883600 -3.95369100 -2.92926200 2.18432000 2.14464000 2.83007200 2.71921100 3.41275700 2.90338100 3.35300800 2.69338500 3.90317300 -0.40323500 0.85091400 -1.40097000 -0.05813800 -1.19755100 -2.22138500 0.03849700 -1.91766700 -1.04650400 1.13103800 -2.06219800 -3.25832000 -1.05194400 0.04262200 -1.80719100 0.27004200 1.28054400 -0.48354500 1.20757500 2.37297600 0.31142600 2.26411100 3.27219000 2.19000600 -4.05852600 3.89364500 1.48980500
SC
5.64133800 4.91522400 6.81239600 5.46703300 6.07520300 7.02286500 7.52042500 6.27978500 -4.61276800 -4.85730800 -5.58612800 -6.01043100 -6.75073000 -5.41513200 -6.95618500 -6.21098400 -7.45747800 -0.24225600 0.55696800 -0.86692200 -0.00565000 -0.72721700 -1.38967000 0.06547400 -1.16963200 -0.61363300 0.76104000 -2.58857800 -0.67985400 -0.60706100 0.08530700 -1.07791500 0.23737300 0.87505100 -0.23044100 0.83909800 1.55495700 0.28270700 1.50420900 2.11451000 1.46416400 8.13320100 -8.05923800 -3.90262000
EP
TE D
M AN U
12.49768900 14.72500600 13.00108100 11.42527300 15.25115100 14.39079400 12.31683700 16.31523300 13.43705900 14.84424800 12.64767600 15.40046100 13.18147300 11.57692700 14.57064400 16.46516500 12.52092600 -13.06283000 -14.15734200 -13.82372100 -15.57465400 -15.21147200 -13.35030200 -17.00884600 -16.47493900 -17.58701400 -18.21447500 -16.55310500 -16.53781700 -18.98767500 -19.54453700 -19.60736400 -20.94013000 -21.63660100 -21.57658000 -23.11497200 -21.01280400 -23.77984700 -23.71261100 -20.48260400 -24.69271200 15.02997300 15.23827100 15.62826300
AC C
C C C H C C H H C C C C C H C H H C S C C C H C C C S F F C C H C C H C C O O N H O O O
S42
ACCEPTED MANUSCRIPT -1.71042500 1.30870000 2.27347000 0.74826300 0.73316200 4.56954900 5.43847000 3.88442500 4.90198200 -4.69015000 -5.53952600 -3.97014200 -5.04611700 -1.58935800 -2.57558500 -1.02682800 -1.03998900
RI PT
3.95797600 -4.15833900 -4.20962100 -5.08819300 -3.30808100 -9.08118600 -8.66568100 -9.54434900 -9.82920400 9.15790100 8.74833300 9.61137600 9.91226600 4.21828700 4.28237000 5.14292400 3.36368500
SC
15.54077900 17.05014800 17.57363300 17.21790400 17.42204500 14.45171600 13.92256700 13.72805100 15.17438200 14.21090500 13.64656000 13.51549300 14.91554500 16.96822800 17.44855300 17.15656000 17.36864400
AC C
EP
TE D
M AN U
O C H H H C H H H C H H H C H H H
S43
ACCEPTED MANUSCRIPT FSQ104
SC
RI PT
0.42216300 -0.25673900 0.50169800 -0.26958100 0.50798800 -0.25252800 1.69059100 -0.67272200 -0.68548300 0.18956000 1.86597700 -0.71795900 2.90379500 -1.12089600 -0.88484600 0.28050600 -1.88625300 0.61501700 0.47605300 -0.19467400 3.16075900 -1.18299200 3.80974100 -1.43582500 3.03538100 -1.18170700 -2.18269800 0.75250600 -2.80793800 0.96163400 -1.99230400 0.63917200 -0.91223300 0.32590400 1.83932400 -0.66956500 3.76158800 -1.38096800 4.81900400 -1.80299500 -2.80610400 0.99314400 -3.81494200 1.32467500 -2.21207600 0.79294100 -0.74279100 0.27900500 1.64243600 -0.57931300 3.14396600 -1.14049300 5.17679700 -1.88728900 -4.22027900 1.50197900 -2.86061400 1.04096300 -1.95953900 0.72500700 0.44390700 -0.14097300 2.84681800 -1.00091100 3.77011900 -1.34580900 6.26881200 -0.98969900 5.45342600 -3.27288700 -4.49358100 2.88835900 -5.31414600 0.60654100 -3.87008100 1.40736900 -2.09507000 0.78378900 0.41065700 -0.11455200 2.96044100 -1.02533600 4.77809200 -1.70522000
TE D
M AN U
6.00361400 4.77777600 3.35116600 2.67861400 2.71285700 1.30159800 3.33864400 1.34097100 3.41365400 -0.14129200 1.07438000 2.34971000 4.40924200 1.15428700 2.45068100 4.48961500 -1.58281200 -1.62452500 -0.19137200 2.46790200 -0.09342300 2.59774500 -1.35251500 -2.95511900 -2.99096600 -1.43237500 -0.20952400 -0.06919200 -2.63268100 -3.62249800 -3.62922800 -3.68982800 -2.72971200 -0.17676800 -0.25829100 -0.02708300 -0.09063600 -2.75163900 -4.69414400 -5.04685900 -4.76400100 -2.87905900
EP
AC C
C C C C C N C N C Zn C C H C C H N N C H C H C C C C C C C C C C C C C C C H H C H H
S44
ACCEPTED MANUSCRIPT
RI PT
-1.45439400 0.35934200 -3.75754500 -4.09846000 3.37605200 3.71129500 1.07418900 -0.74353300 -2.83726800 -0.76254000 1.36246700 -4.82122700 -5.54211400 2.45787500 4.44045100 5.15611300 0.38402500 -1.74400700 -3.20236100 1.31803800 1.24532300 2.32071900 -5.83876400 -5.91184600 -5.95565200 2.82529600 5.46970600 5.56735700 5.51182900 -1.62471500 -1.69879700 -2.70351200 -0.06993100 0.00952800 0.46466500 -0.33006400 0.55413100 0.82834800 -0.24293500 -0.67449600 0.18507800 0.99093900 1.30185600 -0.53127100
SC
7.60269600 5.92227000 6.78030700 4.33071300 -5.81929300 -3.36883300 -6.64695600 -4.97060100 7.84000800 8.43725100 6.97729300 6.98730200 4.51353800 -6.88108800 -6.02377800 -3.54795000 -7.48308100 -6.02785900 8.86416300 7.60481000 7.60360200 6.45608000 5.04882400 5.05234400 3.50350400 -7.90441500 -4.07939700 -2.53688300 -4.08875700 -6.65223400 -6.65689400 -5.50891000 0.31532600 0.11794900 -1.15877200 1.09251500 -1.39267700 -2.19499500 0.86328100 2.06087500 -0.34263500 -2.62065600 -3.51669000 1.68424400
EP
TE D
M AN U
-0.19364700 -0.12823700 -0.27569100 -0.28642300 -0.00647100 -0.00916100 -0.07035700 -0.13265200 -0.24314900 -0.16965300 -0.08713100 -0.31309500 -0.34522200 -0.02863200 0.02392600 0.02577400 -0.08768500 -0.17610200 -0.25663400 -0.98791900 0.80795700 -0.04875900 -1.25771100 0.53805800 -0.36006100 -0.01420100 0.93490500 0.03015000 -0.86196400 -1.07220700 0.72367900 -0.21428400 -6.27470000 -7.66721500 -8.19685500 -8.61628000 -9.65353300 -7.42265200 -10.01361300 -8.26629500 -10.59096100 -9.99492500 -8.49883200 -10.66604100
AC C
C O C O C O C O C H C H C C H C H C H H H H H H H H H H H H H H C C C C C N C H C N S H
S45
ACCEPTED MANUSCRIPT
RI PT
-0.22839400 -0.65444900 0.22406600 -0.64420300 0.25932600 -0.16699500 -0.12945600 -0.72257100 0.56030000 -1.92173000 -0.12955800 1.72723200 0.07995800 -2.50146900 -2.40343600 -0.71889800 0.79642000 2.39135700 2.11635000 0.74997300 -0.83325200 -1.91587200 -3.43658300 -0.22635300 1.92565400 3.29741600 0.33660600 -1.01429500 0.61984600 -2.53774100 -3.53728300 -2.03345700 -3.92381900 -3.98431800 -3.23462500 -4.69161700 2.61298100 2.49046800 3.81543000 3.31271400 1.84484300 4.09291900 3.32661900 -3.36261700
SC
0.29965700 1.36242700 -0.90236200 1.24854600 -1.00708000 0.05372700 -0.08994900 -1.24450800 0.88515300 -1.78732400 -1.88176000 1.50942300 1.26310500 -2.92441900 -1.30207200 -3.01745200 -1.49314200 2.48142500 1.22833800 2.22978600 0.81708700 -3.57309000 -3.29528700 -3.49172900 2.86458100 2.93135500 2.52081200 2.26742300 -1.90851400 -4.76737100 -5.57172100 -5.39447700 -6.67104100 -5.40255500 -6.74815500 -7.38756900 3.87592900 4.14258500 5.02942400 5.22441100 3.56750000 5.82139800 5.54295200 -7.75088700
TE D
M AN U
7.42107500 8.25622500 8.03613700 9.65376100 9.43392800 10.26066200 11.68304500 12.28294800 12.47172800 11.76048600 13.39839700 11.97971600 13.74730600 12.33227800 10.91679400 13.96816000 13.81083100 12.73925300 11.00520400 14.50288200 14.12931900 13.45127800 11.92135400 14.81408800 14.02061700 12.33938200 15.46493700 7.77941100 9.91641200 14.03421300 13.51874300 15.67140800 14.36512100 12.54523400 15.55491100 14.09105500 14.83177600 16.18264800 14.08821800 16.66109600 16.83744200 15.69617400 17.69862000 16.66700400
EP
AC C
C C C C C C N C C C C C C C H C H C H C H C H H C H H H H C C S C H C H C C S C H C H C
S46
ACCEPTED MANUSCRIPT
RI PT
-4.14379400 -3.63477200 -2.42705900 5.06773700 4.79706800 6.08888500 5.08481300 0.25601100 -0.22676400 0.65402600 0.14059000 0.58485700 0.97207000 0.11241500 0.87592700 0.54135400 -0.30848600 2.23007700 0.10594000 0.55154300 0.12565500 0.85096800 0.04426800 -0.34832600 0.34352100 -0.31193300 -0.77986500 0.04328500 -0.72376900 -1.13508300 -0.68924600 0.62707500 -1.10189400 1.09259600 0.30823100 1.99274700 1.33239300 -1.53743600 -2.41292400 -0.72702700 -1.80758200
SC
-8.47969900 -7.27471900 -8.30294300 6.95768700 7.80691000 6.65410100 7.31322300 -0.54162600 0.82415600 -1.67661400 -0.23101800 -1.49036400 -2.57806000 -0.16683600 -2.32969400 -1.39338400 1.01319200 -2.78289900 -3.53248300 -1.44203200 -0.23994400 -2.30214800 -0.02957900 1.07318700 -0.88706800 0.94693000 2.30725400 -0.06944800 2.10331000 3.32375500 1.99077700 -1.91990900 2.23696700 -3.17836600 -3.65389100 -3.02736100 -3.81085500 3.51169200 3.38392100 4.00051100 4.11999800
EP
TE D
M AN U
16.42107600 17.61869700 16.83036800 15.82798300 15.18594700 15.55985400 16.86496400 -12.02416000 -13.16949000 -12.74428200 -14.54927900 -14.13959200 -12.23762200 -15.98645900 -15.37314600 -16.52033100 -17.23603400 -15.41736300 -15.40909700 -17.91998500 -18.52136500 -18.50876200 -19.92528600 -20.66237200 -20.53113100 -22.13689400 -20.08305000 -22.76595100 -22.77677600 -19.58970500 -23.75341100 7.16908900 10.52306500 7.74009200 8.34441200 8.35150800 6.88335000 9.97072000 9.31861100 9.41272100 10.83565700
AC C
H H H C H H H C S C C C H C C C S F F C C H C C H C C O O N H O O C H H H C H H H
S47
ACCEPTED MANUSCRIPT SM315
RI PT
0.01533000 -0.93664200 0.89764000 -1.14244300 -1.86611000 0.94816400 1.90873700 -0.18035400 -2.17342000 -2.62238600 -1.92170300 1.95981400 2.55799200 2.08797900 0.79859100 -1.32766100 -2.71810800 -3.41331300 2.36316600 3.36914000 1.81634400 0.57414600 -1.26081400 -2.31709000 -3.81338200 3.46750300 2.22915100 1.46674800 -0.38214600 -2.22921200 -2.87805700 -3.51053700 -5.17310800 4.81940400 3.18295200 2.99932800 1.49779100 -0.45094700 -2.38242000 -3.66073600 -4.52987500 -2.15230100
SC
0.03904200 -0.86091800 0.84853500 -1.11284600 -1.65471000 0.91545900 1.72848800 -0.19549700 -2.04536500 -2.38696900 -1.65470000 1.81506100 2.32612000 1.86883400 0.70361000 -1.29005200 -2.57478400 -3.08694400 2.17507000 3.03871900 1.66015100 0.48255700 -1.24763600 -2.22256700 -3.59516700 3.18693600 2.03985000 1.31756500 -0.42522200 -2.17507400 -2.77438300 -4.97143600 -3.20862400 2.78279100 4.57154600 2.76281200 1.33968300 -0.50480900 -2.33722200 -3.51827200 -5.94012100 -5.28149100
EP
TE D
M AN U
-3.16256100 -2.62984100 -2.41106300 -1.27539700 -3.41823800 -1.02035400 -2.97604800 0.30876900 -1.19045800 -2.53183600 -4.49662800 -0.69567900 -1.91998800 -4.03160700 1.89074700 1.63656300 0.00332900 -2.75957500 0.61264200 -1.96094200 1.80191600 3.23952400 3.01922800 1.30536500 -0.13357400 0.73935300 3.14668800 4.03444600 3.78211200 3.58488000 2.53007400 -0.25253800 -0.15373000 0.82827900 0.77449200 3.37400200 5.11564700 5.20089500 4.64207100 2.57031900 -0.38868500 -0.22297300
AC C
C C C N C N C Zn C C H C C H N N C H C H C C C C C C C C C C C C C C C H H C H H C O
S48
ACCEPTED MANUSCRIPT
RI PT
-6.20714600 -5.40001800 5.86312700 5.02866700 4.21222600 1.83130900 -5.86902300 -4.29229200 -1.73802300 -7.24855100 -6.76928800 5.54297900 6.89840400 6.38615100 3.98878300 1.43921100 -6.65944800 -2.12795100 -2.06159000 -0.64762300 -7.34840200 -7.27126700 -6.68054900 6.34090300 7.01515600 6.28297200 6.84273000 1.73270200 1.87346600 0.35105100 -0.46198700 -0.41196900 0.52179600 -1.22449400 0.58784500 1.37279200 -1.14848200 -1.94638600 -0.27256000 1.50146900 2.30053400 -1.84364900 -0.24401300 0.19181500
SC
-4.16187200 -1.83800100 3.72688800 1.40503400 5.53147900 4.89936100 -5.51946600 -6.99421300 -6.66953800 -3.86005600 -1.34300900 5.09332600 3.41151600 0.89065200 6.59221800 6.30115900 -6.25895600 -7.29127300 -7.08053800 -6.64602900 -1.75277400 -1.58040900 -0.26045200 5.82607600 1.23933300 -0.19503000 1.17800700 6.77779900 6.85354300 6.29303200 -0.52753600 -0.49494000 0.39246900 -1.27301700 0.45017400 1.20294500 -1.21698000 -1.94256600 -0.39625700 1.32142500 2.08104100 -1.84107500 -0.40506700 0.71662300
TE D
M AN U
-0.28811000 -0.03511400 0.95105900 0.78313700 0.89663900 0.68234400 -0.40421800 -0.47986400 -0.37067900 -0.30381900 -0.04636800 0.98366500 1.01856700 0.89568600 0.92385000 0.71066200 -0.50848700 0.44716400 -1.33685700 -0.32753700 0.79270200 -0.99452800 0.06209000 1.07778500 0.06488700 0.84857700 1.85282900 1.65618700 -0.13411100 0.62480500 6.43103400 7.84387100 8.51898100 8.67062600 9.99733400 7.86683100 10.09404300 8.21248800 10.80752700 10.47568500 9.09128000 10.64777000 12.29182800 13.04484200
EP
AC C
C O C O C O C H C H C C H C H C H H H H H H H H H H H H H H C C C C C N C H C N S H C C
S49
ACCEPTED MANUSCRIPT
RI PT
-0.67600300 0.16934500 0.55282800 -0.69596300 -0.96760700 -0.27810600 0.49752600 -1.02030300 -0.31561100 -0.69225400 0.12368100 0.07949600 0.09198700 0.68671000 -0.42997200 1.71206800 0.24452700 -1.53212300 0.15052000 2.27559900 2.06043500 0.82071100 -0.55412900 -2.02618900 -2.00578100 -0.36106500 1.00870000 1.85608600 3.04364300 0.45470800 -1.45883200 -2.89223700 0.10245900 2.52856200 -1.97972200 1.84077500 3.91665500 -2.40609200 -2.09212100 2.51992500 0.46135700 4.62010800 4.47458400 -2.92510900
SC
-1.55676900 0.69861900 1.59594900 -1.57939900 -2.45260100 -0.44669300 1.56512000 -2.46453700 -0.50951800 -1.48272900 0.66436000 0.57222600 0.14264300 -0.92935900 1.31683900 -1.71094600 -1.26855100 1.99738600 1.84927000 -2.78353000 -1.48389800 -2.33715100 -0.69736400 3.16875800 1.60402400 3.01218900 1.35773400 -3.12131000 -3.37988300 -2.57854100 3.70847700 3.65159000 3.39351500 -4.22535700 4.98413800 -5.13054000 -4.42683900 6.01601200 5.23805600 -6.16383800 -4.94533200 -5.45570500 -3.73734500 7.24105700
TE D
M AN U
13.00637800 14.44552900 12.52690300 14.40347200 12.46616200 15.13812600 15.00967100 14.94308100 16.61622300 17.29712200 17.22499200 18.20326900 -4.60503400 -5.34154300 -5.23376900 -4.76151100 -6.64372400 -4.66747500 -6.41068100 -5.46677200 -3.75869100 -7.34219600 -7.10709800 -5.25783700 -3.77338100 -7.00066000 -6.85886500 -6.77612300 -4.97978300 -8.33344800 -6.43755900 -4.81093800 -7.90333300 -7.51791600 -7.00445500 -8.38381000 -7.37515700 -6.14360100 -8.40633600 -9.04779300 -8.51731200 -8.02907400 -6.74716900 -6.60308600
EP
AC C
C C H C H C H H C O O H N C C C C C C C H C H C H C H C H H C H H C C C C C C C O C H C
S50
ACCEPTED MANUSCRIPT
RI PT
-2.30547300 -2.60599700 -1.68463700 3.90779300 2.00984000 -0.31289500 5.69060500 -3.02260700 -3.22822000 -2.70145200 -1.89073700 4.47414400 -0.20317800 -0.01945800 -1.35055000 -3.51280000 -1.30219700 -2.95343000 -1.54519800 5.90437600 -3.96413700 6.48513100 6.11414200 6.17537600 -4.30472600 -3.14364900 -4.79623900
SC
5.86598800 6.45149000 4.21212100 -6.32725300 -6.85991400 -5.91525200 -5.55131800 7.45192600 7.99843600 6.65518400 4.36429600 -7.38795100 -6.92554200 -5.92064400 -5.58774900 8.61762700 5.20041000 4.51514800 3.42616000 -7.62449300 9.69949700 -6.76012800 -8.48984500 -7.85159100 10.48619700 10.07858300 9.37639900
TE D
M AN U
-5.07198400 -8.88912700 -9.26437700 -8.87070300 -9.70339600 -9.27819800 -7.88307900 -7.98917800 -5.88825100 -9.94928200 -10.69754800 -9.58526200 -8.86067200 -10.33724000 -9.18581600 -8.58696400 -11.10015500 -10.93191600 -11.13688300 -9.45285600 -7.72403300 -9.80413100 -10.08497600 -8.41229500 -8.40042700 -7.09879300 -7.08292300
AC C
EP
H C O C H C H C H H C O H H H O H H H C C H H H H H H
S51
ACCEPTED MANUSCRIPT The Cartesian Coordinates of dye-TiO2 complexes F101-TiO2
RI PT
11.85840000 11.94230000 12.02050000 12.17380000 11.81810000 12.32260000 11.87580000 12.53380000 12.19910000 11.97100000 11.62980000 12.36970000 12.09560000 11.64080000 12.86290000 12.77720000 12.42800000 11.94080000 12.63320000 12.06970000 12.86720000 13.12840000 13.04860000 12.69040000 12.38480000 12.66370000 13.14610000 13.30770000 13.21800000 13.13890000 12.91870000 11.16940000 13.55290000 11.49980000 13.85920000 13.20980000 13.52880000 13.49770000 13.34330000 12.90740000 11.11360000
SC
11.93610000 10.94330000 11.73780000 9.60120000 11.18360000 10.52930000 12.76410000 8.71010000 8.98810000 9.97140000 12.14850000 10.76790000 12.16230000 13.80510000 7.81590000 6.89730000 7.61630000 9.75950000 9.80430000 12.61850000 8.43980000 6.48880000 5.68850000 6.65380000 7.15630000 10.27530000 7.46350000 6.25310000 5.48020000 4.65070000 5.24930000 6.75380000 7.12620000 10.25170000 10.74570000 7.68200000 5.28900000 4.17230000 3.60520000 4.78550000 6.33610000
TE D
M AN U
7.61960000 8.61860000 6.23270000 8.38500000 10.03830000 5.63500000 5.22500000 6.56780000 9.62370000 10.65840000 10.49730000 4.27480000 4.01380000 5.41980000 4.75020000 7.50720000 9.85930000 11.72230000 3.27910000 3.02940000 3.50950000 4.51540000 6.91310000 8.87160000 11.28430000 1.85750000 2.47920000 3.09900000 5.51590000 7.91410000 9.12660000 11.87470000 12.07270000 1.06270000 1.27740000 1.41810000 2.64890000 5.06170000 7.70720000 10.10770000 13.21580000
EP
AC C
C C C N C N C Zn C C H C C H N N C H C H C C C C C C C C C C C C C C C H H C H H C
S52
ACCEPTED MANUSCRIPT
RI PT
10.07140000 13.51550000 14.70220000 11.52240000 10.36890000 13.90040000 14.95530000 12.29190000 10.17390000 8.79960000 14.41840000 15.92070000 12.72680000 10.62260000 9.16120000 14.82580000 16.20420000 12.25610000 8.80430000 8.53360000 8.08050000 16.16570000 15.85000000 16.69190000 12.75140000 8.85370000 8.40670000 9.28620000 16.52140000 16.13290000 16.92300000 13.74260000 14.02100000 14.11540000 14.21990000 14.40120000 13.94880000 14.49600000 14.15800000 14.59910000 14.45440000 14.15040000 14.63440000 11.58440000
SC
6.80630000 6.71190000 7.53610000 10.67860000 9.78210000 11.17660000 10.73760000 6.32180000 6.02680000 6.43500000 6.69290000 7.52940000 11.13720000 10.65710000 9.70860000 11.53610000 11.19990000 5.99910000 5.38520000 7.09340000 6.56360000 6.51370000 8.21300000 7.88120000 11.46970000 10.70530000 9.30760000 9.02950000 10.57000000 12.25050000 11.10960000 3.05840000 1.82590000 1.74120000 0.63230000 0.46760000 2.79110000 -0.59060000 0.64890000 -0.74080000 0.53750000 2.17750000 -1.46600000 13.27890000
TE D
M AN U
11.04270000 13.41560000 11.42960000 -0.27630000 1.69770000 -0.06000000 2.11400000 13.96870000 13.66750000 11.60980000 14.02150000 12.19860000 -0.81930000 -0.88650000 0.91500000 -0.50420000 1.56390000 15.00990000 11.93980000 12.45030000 10.79500000 12.54420000 13.05820000 11.50620000 -1.85790000 0.56380000 1.59880000 0.05850000 0.71940000 1.24420000 2.38450000 4.59890000 3.98670000 2.54430000 4.68900000 1.87800000 1.73760000 4.04280000 5.77640000 2.65470000 0.54350000 0.15330000 4.67860000 8.05760000
EP
AC C
O C O C O C O C H C H C C H C H C H H H H H H H H H H H H H H C C C C C N C H C N S H N
S53
ACCEPTED MANUSCRIPT
RI PT
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SC
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TE D
M AN U
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AC C
C C C C C C C H C H C H C H C H H C H H C C C C C C C O C H C H C O C H C H C H H C O H
S54
ACCEPTED MANUSCRIPT
RI PT
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SC
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TE D
M AN U
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EP
AC C
H H O H H H C C H H H H H H C S C C C H C C C S F F C C H C O O Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti
S55
ACCEPTED MANUSCRIPT
RI PT
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TE D
M AN U
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EP
AC C
Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti O O O O O O O O O O O O O O O O O O
S56
ACCEPTED MANUSCRIPT
RI PT
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TE D
M AN U
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EP
AC C
O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O
S57
ACCEPTED MANUSCRIPT 11.58130000 12.25970000 12.20020000 22.16310000 22.35680000 22.22370000 17.06360000 16.85470000 17.21620000 17.65790000 17.23190000 17.27040000 17.09990000 17.57190000 16.69750000
RI PT
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AC C
EP
TE D
M AN U
O O O O O O O O O O O O O O H
S58
ACCEPTED MANUSCRIPT F102-TiO2
RI PT
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SC
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TE D
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EP
AC C
C C C N C N C Zn C C H C C H N N C H C H C C C C C C C C C C C C C C C H H C H H C
S59
ACCEPTED MANUSCRIPT
RI PT
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EP
AC C
O C O C O C O C H C H C C H C H C H H H H H H H H H H H H H H C C C C C N C H C N S H N
S60
ACCEPTED MANUSCRIPT
RI PT
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SC
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EP
TE D
M AN U
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AC C
C C C C C C C H C H C H C H C H H C H H C C C C C C C O C H C H C O C H C H C H H C O H
S61
ACCEPTED MANUSCRIPT
RI PT
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SC
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EP
TE D
M AN U
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AC C
H H O H H H C C H H H H H H C C S C H C Si C C C C S C C C C C C H C H C H C H C H C C H
S62
ACCEPTED MANUSCRIPT
RI PT
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TE D
M AN U
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EP
AC C
H C H H O O H H Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti
S63
ACCEPTED MANUSCRIPT
RI PT
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TE D
M AN U
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EP
AC C
Ti Ti O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O
S64
ACCEPTED MANUSCRIPT
RI PT
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TE D
M AN U
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EP
AC C
O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O H
S65
ACCEPTED MANUSCRIPT F103-TiO2
RI PT
12.69470000 12.84700000 12.77210000 13.07650000 12.80440000 13.04610000 12.55720000 13.33070000 13.18280000 13.00900000 12.63360000 13.00560000 12.70670000 12.32660000 13.55300000 13.64470000 13.43770000 13.04550000 13.20890000 12.61490000 13.46900000 13.81550000 13.89110000 13.64480000 13.50120000 13.12570000 13.68500000 13.90260000 13.97660000 14.05260000 13.89940000 12.33780000 14.72490000 11.90200000 14.26640000 13.67350000 14.10190000 14.24350000 14.25430000 13.95200000 12.38690000
SC
9.80980000 8.70980000 9.77490000 7.40730000 8.78240000 8.64750000 10.90770000 6.73670000 6.65650000 7.51030000 9.68500000 9.04110000 10.45230000 11.91580000 6.06280000 4.83160000 5.27050000 7.17740000 8.20130000 11.01760000 6.82320000 4.77560000 3.70320000 4.43220000 4.64640000 8.82810000 5.97470000 4.70560000 3.66060000 2.55970000 3.01170000 4.15300000 4.54690000 8.87130000 9.38310000 6.31260000 3.80230000 2.42000000 1.54830000 2.43840000 3.58000000
TE D
M AN U
9.47160000 10.34220000 8.06400000 9.94180000 11.78500000 7.31340000 7.19250000 8.01470000 11.09790000 12.25090000 12.36290000 5.98920000 5.90890000 7.52010000 6.08900000 8.72070000 11.15780000 13.28340000 4.87430000 4.98690000 4.93040000 5.68710000 7.97550000 10.05040000 12.51840000 3.51640000 3.77920000 4.24470000 6.55620000 8.84310000 10.12710000 13.14360000 13.21170000 2.81780000 2.90150000 2.74770000 3.67390000 5.93470000 8.50570000 11.04700000 14.42640000
EP
AC C
C C C N C N C Zn C C H C C H N N C H C H C C C C C C C C C C C C C C C H H C H H C
S66
ACCEPTED MANUSCRIPT
RI PT
11.17980000 14.79270000 15.81910000 11.81250000 10.82980000 14.19540000 15.42660000 13.61820000 11.48650000 9.96010000 15.73880000 17.09150000 12.96500000 10.86620000 9.56420000 15.07810000 16.62120000 13.66300000 10.00400000 9.74980000 9.17900000 17.37140000 17.07870000 17.80620000 12.90330000 9.22240000 8.86950000 9.62620000 16.87400000 16.51310000 17.40630000 14.47420000 14.73450000 14.81370000 14.93050000 15.08790000 14.64930000 15.19330000 14.87970000 15.28430000 15.13500000 14.83830000 15.33330000 12.43410000
SC
4.28120000 3.97690000 5.05190000 9.44580000 8.31450000 9.96150000 9.30220000 3.49990000 3.20180000 3.81680000 3.90460000 4.97580000 9.98490000 9.47710000 8.30850000 10.38700000 9.84690000 3.05580000 2.73610000 4.36610000 4.02350000 3.93100000 5.55050000 5.42170000 10.43320000 9.33300000 7.82050000 7.73300000 9.32130000 10.92500000 9.67930000 1.37380000 0.22600000 0.32340000 -1.04600000 -0.85710000 1.46940000 -2.17850000 -1.16780000 -2.15410000 -0.61540000 1.06240000 -3.12920000 11.08900000
TE D
M AN U
12.40670000 14.49470000 12.54050000 1.53840000 3.48290000 1.62250000 3.64240000 15.08490000 14.90520000 13.01740000 15.02630000 13.21210000 0.95770000 1.00330000 2.79420000 1.15050000 3.04930000 16.08020000 13.21940000 13.94760000 12.27960000 13.41480000 14.15040000 12.51340000 -0.03480000 2.58380000 3.48490000 1.85860000 2.11610000 2.85700000 3.79310000 5.32970000 4.56260000 3.12000000 5.10600000 2.29410000 2.45650000 4.30540000 6.18740000 2.91060000 0.97880000 0.80620000 4.82130000 10.07710000
EP
AC C
O C O C O C O C H C H C C H C H C H H H H H H H H H H H H H H C C C C C N C H C N S H N
S67
ACCEPTED MANUSCRIPT
RI PT
11.15910000 13.46310000 10.01980000 11.00100000 14.81260000 13.17160000 8.76820000 10.11910000 9.74330000 11.86970000 15.82970000 15.06210000 14.19670000 12.13560000 8.58980000 7.91030000 9.65360000 15.55480000 16.86390000 13.93990000 7.23070000 16.66700000 6.94460000 6.13610000 17.81970000 16.65470000 5.64090000 8.01510000 4.82050000 6.32570000 18.91760000 17.84800000 17.73660000 15.53330000 4.57970000 5.40950000 7.72390000 4.01900000 18.86670000 19.77670000 17.74020000 15.55290000 3.33770000 7.02800000
SC
11.32580000 12.06700000 10.67740000 12.17430000 11.67120000 13.44370000 10.88470000 10.00250000 12.37970000 12.67440000 12.62510000 10.61430000 14.38850000 13.77390000 11.74630000 10.34720000 13.03910000 14.00660000 12.28790000 15.44260000 11.99130000 14.98150000 12.13120000 12.08600000 14.66090000 16.25560000 12.34810000 12.01410000 12.30310000 12.01400000 15.52200000 13.70380000 17.13250000 16.56390000 12.43340000 12.44830000 12.02740000 12.37930000 16.76720000 15.21810000 18.10620000 17.80200000 12.65440000 11.21740000
TE D
M AN U
10.65310000 10.07230000 10.13880000 11.76890000 10.13700000 9.97800000 10.71840000 9.28930000 12.33340000 12.19610000 10.10510000 10.22370000 9.96270000 9.90500000 11.82130000 10.31290000 13.19400000 10.01980000 10.18580000 9.88410000 12.36010000 9.93250000 13.74830000 11.48400000 9.19630000 10.56840000 14.20240000 14.61520000 11.91430000 10.41270000 9.06910000 8.67480000 10.45410000 11.31550000 13.28650000 15.25980000 16.02630000 11.18270000 9.70580000 8.47490000 10.93720000 12.05220000 13.85180000 16.29180000
EP
AC C
C C C C C C C H C H C H C H C H H C H H C C C C C C C O C H C H C O C H C H C H H C O H
S68
ACCEPTED MANUSCRIPT
RI PT
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SC
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TE D
M AN U
16.33800000 16.51590000 9.66170000 11.37400000 12.75500000 12.60570000 12.94180000 8.90420000 12.24490000 13.57680000 12.37750000 8.99510000 7.84550000 9.32200000 2.14210000 2.98350000 0.76610000 1.44880000 0.38230000 0.07370000 -0.64530000 1.38980000 0.33150000 2.64220000 -1.48690000 1.80450000 4.93340000 8.22150000 -1.86230000 5.05130000 8.28600000 -2.09050000 1.59770000 5.10600000 8.44930000 -3.76020000 -0.12960000 3.60150000 7.12300000 -3.40890000 -0.01790000 3.58640000 7.20640000 -2.01730000
EP
AC C
H H O H H H C C H H H H H H C S C C C H H C O O Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti
S69
ACCEPTED MANUSCRIPT
RI PT
11.73600000 11.36580000 11.42090000 11.47990000 11.65140000 11.67560000 21.22380000 21.58900000 21.46380000 21.41560000 17.04320000 16.85150000 16.72690000 16.45110000 16.91390000 16.89620000 16.64250000 16.63230000 11.43870000 11.56810000 10.88920000 11.31260000 21.06510000 21.12540000 21.04700000 20.99620000 21.06990000 20.99640000 20.96550000 15.62110000 15.97710000 15.87000000 15.90490000 17.03920000 16.53600000 16.40440000 16.19720000 13.73550000 13.84750000 13.40390000 13.20470000 13.61060000 13.74120000 14.25280000
SC
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TE D
M AN U
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EP
AC C
Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti O O O O O O O O O O O O O O O O O O O O O O O O O O
S70
ACCEPTED MANUSCRIPT
RI PT
13.26450000 8.72620000 8.43190000 8.52890000 18.75440000 18.67950000 18.60670000 19.63000000 18.55660000 18.77100000 18.76700000 18.80660000 13.69360000 14.84370000 14.39090000 14.46200000 15.11650000 15.14210000 14.89820000 14.90000000 9.89380000 9.97650000 9.51430000 9.79050000 9.69160000 9.86440000 9.85490000 19.34830000 19.77540000 19.41500000 19.55570000 12.24150000 12.24020000 12.11850000 11.25670000 12.02160000 11.56190000 12.24150000 12.18360000 22.15060000 22.34330000 22.21060000 17.05590000 16.85040000
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TE D
M AN U
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EP
AC C
O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O
S71
ACCEPTED MANUSCRIPT 5.59990000 -13.00570000 8.67330000 -13.18590000 -2.02980000 -10.33490000 1.61280000 -9.26300000 5.30830000 -9.37680000 9.01330000 -9.34520000 5.31590000 -8.36790000
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AC C
EP
TE D
M AN U
SC
RI PT
O O O O O O H
S72
ACCEPTED MANUSCRIPT F104-TiO2
TE D
M AN U
SC
RI PT
2.07640000 13.90090000 10.38290000 0.75130000 13.43110000 10.50220000 3.25150000 13.14660000 10.58170000 0.39590000 12.14510000 10.86020000 -0.43450000 14.21850000 10.24910000 3.28580000 11.80240000 10.89820000 4.59730000 13.66940000 10.50460000 1.67070000 10.57660000 11.23550000 -0.98620000 12.10080000 10.83790000 -1.50850000 13.39490000 10.46260000 -0.44260000 15.26310000 9.95560000 4.62060000 11.46480000 11.02590000 5.44300000 12.62610000 10.77550000 4.85750000 14.69640000 10.27050000 2.94380000 9.02060000 11.64120000 0.05360000 9.34600000 11.54420000 -1.77800000 10.96880000 11.12050000 -2.56210000 13.63700000 10.36770000 5.11680000 10.18760000 11.36170000 6.52750000 12.64010000 10.81070000 4.33090000 9.05940000 11.63890000 2.59640000 7.73280000 11.96770000 0.08410000 8.01630000 11.88870000 -1.28630000 9.69620000 11.45260000 -3.26510000 11.13690000 11.05480000 6.60230000 10.01410000 11.44370000 4.85260000 7.75300000 11.97400000 3.77970000 6.92760000 12.17830000 1.26440000 7.24990000 12.08880000 -1.26020000 7.50410000 12.02040000 -2.10840000 8.54450000 11.74830000 -3.99900000 11.54630000 12.18670000 -3.96610000 10.90020000 9.85460000 7.28370000 10.20220000 12.66330000 7.35330000 9.64580000 10.30900000 5.90680000 7.50400000 12.04190000 3.77930000 5.87420000 12.44610000 1.12760000 5.89120000 12.44430000 -1.51160000 6.48230000 12.28630000 -3.19350000 8.53920000 11.74980000 -5.39310000 11.71920000 12.12810000
EP
AC C
C C C N C N C Zn C C H C C H N N C H C H C C C C C C C C C C C C C C C H H C H H C
S73
ACCEPTED MANUSCRIPT
RI PT
13.32470000 9.77730000 8.79020000 12.75630000 13.72860000 10.38320000 9.15400000 10.91970000 13.00390000 14.49810000 8.84790000 7.53910000 11.61020000 13.69970000 15.00640000 9.50600000 7.96960000 10.86760000 14.82510000 14.31740000 15.26430000 7.63680000 7.16750000 6.84880000 11.67460000 14.97390000 15.69590000 15.33410000 8.10750000 7.69220000 7.18750000 12.75460000 13.10760000 13.26810000 13.32600000 13.64040000 13.09430000 13.68520000 13.21620000 13.85640000 13.75490000 13.39740000 13.83650000 10.02380000
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TE D
M AN U
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EP
AC C
O C O C O C O C H C H C C H C H C H H H H H H H H H H H H H H C C C C C N C H C N S H N
S74
ACCEPTED MANUSCRIPT
RI PT
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SC
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TE D
M AN U
1.95030000 2.71430000 2.10110000 1.45950000 2.37300000 3.54300000 1.78230000 2.46160000 1.15240000 1.31680000 2.84930000 1.72330000 4.00140000 3.83890000 1.31090000 1.88760000 0.77420000 3.67220000 2.54240000 4.64330000 1.05550000 4.19970000 -0.02720000 1.90300000 4.58280000 4.34000000 -0.22460000 -0.87760000 1.72560000 2.75910000 5.07880000 4.51530000 4.83460000 3.94050000 0.65080000 -1.05040000 -2.04410000 2.42580000 5.20330000 5.36720000 4.94250000 3.96940000 0.35750000 -2.66520000
EP
AC C
C C C C C C C H C H C H C H C H H C H H C C C C C C C O C H C H C O C H C H C H H C O H
S75
ACCEPTED MANUSCRIPT
RI PT
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SC
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TE D
M AN U
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EP
AC C
H H O H H H C C H H H H H H C S C C C H C H C S C H C H C O O Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti
S76
ACCEPTED MANUSCRIPT
RI PT
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TE D
M AN U
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EP
AC C
Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti O O O O O O O O O O O O O O O O O O O
S77
ACCEPTED MANUSCRIPT
RI PT
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TE D
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EP
AC C
O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O
S78
ACCEPTED MANUSCRIPT 12.22780000 12.17230000 22.13920000 22.33310000 22.20060000 17.04560000 16.84310000 17.20560000 17.65410000 17.20030000 17.25320000 17.06490000 17.53580000 16.72090000
RI PT
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AC C
EP
TE D
M AN U
O O O O O O O O O O O O O H
S79
ACCEPTED MANUSCRIPT F105-TiO2
TE D
M AN U
SC
RI PT
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EP
AC C
C C C N C N C Zn C C H C C H N N C H C H C C C C C C C C C C C C C C C H H C H H C
S80
ACCEPTED MANUSCRIPT
RI PT
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SC
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TE D
M AN U
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EP
AC C
O C O C O C O C H C H C C H C H C H H H H H H H H H H H H H H C C C C C N C H C N S H N
S81
ACCEPTED MANUSCRIPT
RI PT
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EP
AC C
C C C C C C C H C H C H C H C H H C H H C C C C C C C O C H C H C O C H C H C H H C O H
S82
ACCEPTED MANUSCRIPT
RI PT
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TE D
M AN U
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EP
AC C
H H O H H H C C H H H H H H C C S H C C S C C H C O O Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti
S83
ACCEPTED MANUSCRIPT
RI PT
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TE D
M AN U
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EP
AC C
Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti O O O O O O O O O O O O O O O O O O O O O O O
S84
ACCEPTED MANUSCRIPT
RI PT
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M AN U
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EP
AC C
O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O
S85
ACCEPTED MANUSCRIPT 22.20440000 17.05310000 16.84750000 17.20780000 17.65410000 17.21110000 17.25690000 17.06900000 17.54240000 16.58490000
RI PT
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AC C
EP
TE D
M AN U
SC
O O O O O O O O O H
S86
ACCEPTED MANUSCRIPT FSQ101-TiO2
SC
RI PT
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EP
TE D
M AN U
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AC C
C C C N C N C Zn C C H C C H N N C H C H C C C C C C C C C C C C C C C H H C H H C
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ACCEPTED MANUSCRIPT
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EP
TE D
M AN U
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ACCEPTED MANUSCRIPT
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S98
ACCEPTED MANUSCRIPT 22.15090000 22.34370000 22.21210000 17.05980000 16.85410000 17.21250000 17.65700000 17.21290000 17.25360000 17.08270000 17.55410000 16.59330000
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S99
ACCEPTED MANUSCRIPT FSQ103-TiO2
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AC C
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S100
ACCEPTED MANUSCRIPT
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S101
ACCEPTED MANUSCRIPT
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AC C
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S102
ACCEPTED MANUSCRIPT
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AC C
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ACCEPTED MANUSCRIPT
RI PT
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AC C
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S105
ACCEPTED MANUSCRIPT
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AC C
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S106
ACCEPTED MANUSCRIPT FSQ104-TiO2
RI PT
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AC C
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S107
ACCEPTED MANUSCRIPT
RI PT
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AC C
H C O C O C O C O C H C H C C H C H C H H H H H H H H H H H H H H C C C C C N C H C N S
S108
ACCEPTED MANUSCRIPT
RI PT
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TE D
M AN U
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EP
AC C
H C C C C C C N C C C C C C C H C H C H C H C H H C H H H H C C S C H C H C C S C H C H
S109
ACCEPTED MANUSCRIPT
RI PT
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SC
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TE D
M AN U
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EP
AC C
C H H H C H H H C S C C C H C C C S F F C C H C C H C C O O N O O C H H H C H H H Ti Ti Ti
S110
ACCEPTED MANUSCRIPT
RI PT
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SC
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TE D
M AN U
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EP
AC C
Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti O O O O O O O O O
S111
ACCEPTED MANUSCRIPT
RI PT
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TE D
M AN U
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EP
AC C
O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O
S112
ACCEPTED MANUSCRIPT 19.33470000 19.76420000 19.40550000 19.54740000 12.23810000 12.24120000 12.12300000 11.26600000 12.00050000 11.54400000 12.22630000 12.17200000 22.13780000 22.33280000 22.20140000 17.04620000 16.84520000 17.20680000 17.65570000 17.19640000 17.24970000 17.06510000 17.53600000 16.70700000
RI PT
-18.22410000 -17.46830000 -17.76760000 -17.84590000 -21.77640000 -22.34360000 -22.53970000 -22.87250000 -16.85400000 -17.15560000 -17.48660000 -17.32500000 -17.90700000 -17.44500000 -17.79680000 -19.77670000 -20.48740000 -19.73990000 -19.93980000 -17.01500000 -15.96180000 -16.11060000 -16.10160000 -15.10830000
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AC C
EP
TE D
M AN U
O O O O O O O O O O O O O O O O O O O O O O O H
S113
ACCEPTED MANUSCRIPT SM315-TiO2
TE D
M AN U
SC
RI PT
1.04780000 11.07290000 11.87660000 -0.13880000 10.41570000 11.48320000 2.15050000 10.48460000 12.53190000 -0.41350000 9.08440000 11.70130000 -1.22120000 11.03120000 10.75340000 2.24690000 9.15390000 12.87350000 3.31740000 11.19770000 12.99200000 0.82110000 7.70020000 12.58840000 -1.64300000 8.83920000 11.12390000 -2.15380000 10.05300000 10.53670000 -1.26580000 12.07370000 10.45280000 3.44390000 9.00800000 13.54360000 4.11730000 10.28010000 13.61830000 3.50890000 12.25720000 12.85150000 2.03980000 6.32850000 13.50410000 -0.59220000 6.24230000 12.27360000 -2.30790000 7.59600000 11.09480000 -3.10530000 10.14150000 10.01930000 3.94160000 7.81040000 14.09370000 5.08010000 10.44780000 14.09220000 3.28710000 6.56680000 14.05320000 1.78150000 4.99650000 13.70160000 -0.51170000 4.92270000 12.64070000 -1.81450000 6.40020000 11.64450000 -3.63770000 7.54760000 10.40910000 5.25650000 7.86840000 14.80550000 3.81850000 5.34130000 14.59840000 2.88760000 4.36310000 14.37900000 0.59150000 4.32190000 13.30680000 -1.70690000 4.22300000 12.24380000 -2.51340000 5.13920000 11.62370000 -4.81930000 7.88800000 11.09980000 -3.72800000 7.17720000 9.05150000 5.29690000 8.02510000 16.20730000 6.47140000 7.74310000 14.10140000 4.78460000 5.24540000 15.08660000 2.93330000 3.31140000 14.65230000 0.52420000 2.94650000 13.61880000 -1.89760000 3.16800000 12.41950000 -3.49560000 4.97940000 11.18800000 -6.06460000 7.86720000 10.44810000
EP
AC C
C C C N C N C Zn C C H C C H N N C H C H C C C C C C C C C C C C C C C H H C H H C
S114
ACCEPTED MANUSCRIPT
RI PT
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SC
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TE D
M AN U
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EP
AC C
O C O C O C O C H C H C C H C H C H H H H H H H H H H H H H H C C C C C N C H C N S H C
S115
ACCEPTED MANUSCRIPT
RI PT
15.49300000 15.87240000 15.80330000 15.21860000 16.17750000 15.93340000 16.14430000 15.76250000 16.44920000 16.42020000 16.59390000 16.43600000 11.59010000 12.33440000 10.60100000 13.65610000 11.77170000 9.48860000 10.70560000 14.38590000 14.10510000 12.51530000 10.74320000 8.51770000 9.37900000 9.72540000 11.57450000 13.84520000 15.40140000 12.05560000 8.60420000 7.64790000 9.84690000 14.67820000 7.57320000 14.19000000 16.02900000 7.01670000 7.07400000 15.03280000 12.87350000 16.88970000 16.41840000 6.01780000
SC
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TE D
M AN U
2.28120000 -0.10790000 2.33420000 3.19350000 -0.05370000 -1.06560000 1.17120000 3.28560000 -0.95790000 1.21410000 0.09160000 2.36310000 1.13990000 0.33820000 2.05270000 -0.03020000 -0.14610000 2.32130000 2.73770000 -0.84260000 0.31500000 -0.95070000 0.11060000 3.23250000 1.79330000 3.64440000 2.57310000 -1.31780000 -1.12940000 -1.30310000 3.92280000 3.38890000 4.16910000 -2.13250000 4.91650000 -3.27430000 -1.80610000 5.74030000 5.08610000 -4.02390000 -3.60000000 -2.54150000 -0.91610000 6.68430000
EP
AC C
C C C H C H C H H C O O N C C C C C C C H C H C H C H C H H C H H C C C C C C C O C H C
S116
ACCEPTED MANUSCRIPT
RI PT
7.40160000 6.08140000 7.60330000 16.38150000 14.68130000 12.37270000 17.92450000 5.54720000 5.63790000 5.68270000 7.08530000 17.10580000 12.92510000 12.42420000 11.32560000 4.57400000 7.26100000 6.00870000 7.63270000 18.49010000 3.98110000 18.61360000 18.88200000 19.03730000 3.23140000 4.72900000 3.48790000 9.41950000 9.27450000 8.92020000 9.25870000 19.11150000 19.67030000 19.39010000 19.16740000 19.55920000 20.01790000 19.24180000 13.84580000 14.25610000 13.98080000 14.19060000 13.60740000 14.48990000
SC
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TE D
M AN U
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EP
AC C
H C O C H C H C H H C O H H H O H H H C C H H H H H H Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti
S117
ACCEPTED MANUSCRIPT
RI PT
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TE D
M AN U
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EP
AC C
Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti O O O O O O O O O O O O O O O O O O O O O O O
S118
ACCEPTED MANUSCRIPT
RI PT
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TE D
M AN U
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EP
AC C
O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O
S119
ACCEPTED MANUSCRIPT 22.36460000 17.00870000 17.08630000 17.57930000 17.61410000 17.14620000 17.61440000 16.73810000 17.47760000 16.81910000
RI PT
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AC C
EP
TE D
M AN U
SC
O O O O O O O O O H
S120
ACCEPTED MANUSCRIPT The Cartesian Coordinates of TiO2 cluster
RI PT
9.54280000 9.50650000 9.09080000 9.46520000 19.17340000 19.34140000 19.40980000 19.15040000 19.20180000 19.17880000 19.20710000 13.88420000 14.27540000 14.14020000 14.16890000 13.68700000 14.60160000 14.08920000 14.09590000 11.72940000 11.74470000 11.37690000 11.42990000 11.46770000 11.64900000 11.67430000 21.20540000 21.55730000 21.43230000 21.40140000 17.04120000 16.85300000 16.72000000 16.44910000 16.88930000 16.86760000 16.62730000 16.61630000 11.43710000 11.57220000 10.90010000 11.31910000
SC
3.81910000 3.64190000 2.93220000 3.66400000 3.52890000 3.94090000 3.95250000 7.27620000 7.93050000 7.75860000 7.60440000 2.78440000 1.99470000 2.11460000 2.21640000 6.18510000 5.61290000 5.88870000 6.16500000 2.11680000 1.80010000 1.49610000 1.74660000 5.88050000 5.63440000 5.41930000 5.46680000 6.57860000 5.96590000 5.88610000 3.46810000 3.13530000 3.45500000 3.78990000 6.84310000 7.10000000 7.22790000 7.48570000 3.91350000 3.66520000 3.25420000 3.55170000
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4.49830000 7.78790000 10.91570000 14.20650000 4.12080000 11.02330000 14.25730000 3.91770000 7.60930000 11.09990000 14.42650000 2.22320000 5.84700000 9.57880000 13.09970000 2.59420000 5.98160000 9.58200000 13.18670000 3.96100000 7.52620000 10.98510000 14.28120000 4.36800000 7.78490000 14.23020000 4.60560000 7.72810000 10.97530000 14.35690000 2.28850000 5.96970000 9.56010000 13.19290000 2.21350000 5.87780000 9.44950000 13.19610000 4.70740000 7.69010000 10.88000000 13.62560000
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Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti O O O O
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21.06060000 21.11530000 21.04840000 20.96750000 21.02200000 20.94920000 20.95170000 15.62520000 15.98550000 15.87730000 15.91290000 17.02510000 16.52750000 16.38150000 16.18500000 13.73800000 13.85680000 13.41300000 13.21350000 13.60330000 13.74390000 14.25170000 13.26070000 8.72800000 8.44070000 8.53860000 18.75650000 18.68320000 18.60080000 19.63160000 18.52580000 18.73270000 18.70650000 18.77480000 13.68510000 14.84460000 14.39990000 14.45990000 15.09250000 15.13090000 14.90590000 14.87910000 9.89730000 9.98500000
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4.00320000 10.71280000 15.16930000 3.63400000 7.51860000 11.16880000 15.16210000 1.80350000 5.61220000 9.89630000 13.21260000 1.51240000 6.23810000 9.38590000 13.41720000 4.01730000 7.66080000 11.40660000 14.62300000 4.32450000 7.52550000 11.37170000 14.96400000 6.09250000 9.27610000 12.63820000 2.39840000 5.60180000 9.60340000 12.74540000 2.23230000 5.58870000 9.41140000 12.89230000 1.73410000 5.99080000 9.54820000 13.15710000 2.10740000 5.69850000 9.31320000 13.35750000 3.71830000 7.55900000
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1.18920000 2.13070000 5.53430000 5.47680000 5.31890000 5.44270000 6.21290000 5.89520000 5.82230000 1.87680000 1.31910000 1.13220000 0.80750000 6.80240000 6.51010000 6.18720000 6.35100000 5.77290000 6.23690000 5.87980000 3.88370000 3.17210000 3.92300000 3.73320000 6.63770000 7.71850000 7.54100000 7.57410000
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10.80470000 15.16760000 3.88580000 8.00510000 14.84940000 4.71860000 7.80480000 10.96390000 13.73500000 2.18120000 5.65160000 9.30340000 12.80190000 2.79290000 6.03610000 9.40970000 12.82950000 6.16350000 9.36110000 12.72660000 4.04100000 7.75630000 11.57830000 14.64620000 3.98020000 7.62740000 11.30930000 14.99010000
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Table 1. Calculated electronic transition data in termed of excitation energies (E/eV), band wavelengths (λ/nm), oscillator Strengths (f), and electronic compositions for the dyes in THF using TD-CAM-B3LYP/LANL2DZ on the PCM model.a Dyes E(eV) λ(nm) f Composition F101 1.76(S0→S1) 703 1.5806 H→L(65%) H→L+1(11%) H-1→L(10%) 3.16(S0→S9) 393 1.1076 H-2→L+3(38%) H→L+3(9%) H-2→L+2(9%) H-2→L+1(8%) H→L+2(8%) H-1→L(6%) F102 1.80(S0→S1) 688 1.5197 H →L(67%) H →L+1(10%) H-1→L(10%) H-2→L+2(5%) 3.16(S0→S8) 392 0.9155 H-2→L+2(50%) H→L+1(22%) H-1→L+1(6%) H-1→L+1(5%) 679 1.2013 H→L(66%) F103 1.82(S0→S1) H→L+1(12%) H-1→L(9%) H-2→L+2(6%) 3.19(S0→S8) 389 1.1700 H-1→L+2(45%) H-4→L(12%) H-1→L+1(11%) H→L+1(8%) 685 1.4463 H→L(67%) F104 1.81(S0→S1) H→L+1(11%) H-1→L(9%) H-2→L+2(5%) 3.13(S0→S7) 396 1.7063 H-2→L+2(36%) H→L+3(15%) H-3→L+3(12%) H-1→L+1(8%) H-1→L+3(6%) H→L+1(5%) F105 1.81(S0→S1) 684 1.3446 H→ L(67%) H→L+1(11%) H-1→L(9%) H-2→L+2(6%) 3.16(S0→S7) 392 1.2668 H-2→L+2(38%) H-2→L+1(11%) H→L+1(9%) H-1→L+1(9%) H→L+2(5%) H-4→L(5%) FSQ101 1.60(S0→S1) 773 2.4426 H→L(60%) H→L+1(13%) H-1→L(11%) H-3→L(5%) 2.81(S0→S7) 441 1.0833 H-2→L+3(19%) H→L+1(17%) H-1→L(17%) H-3→L(13%) H-1→L+2(12%) H-1→L+1(6%) FSQ102 1.62(S0→S1) 764 2.3902 H→ L(57%) H→L+1 (13%) H-1→L(12%) H-3→L(6%) 3.07(S0→S8) 403 1.0409 H-2→L+3(41%) H-1→L(31%) H→L+2(11%) H-3→L(5%) FSQ103 1.64(S0→S1) 756 2.4606 H→ L(57%) H→L+1(15%) H-1→L(9%) 3.13(S0→S10) 396 0.9169 H-2→L+2(35%) H→L+3(31%) H-2→L+1(26%) FSQ104 1.64(S0→S1) 757 2.3918 H→ L(58%) H→L+1(13%) H-1→L(10%) H-3→L(7%) 3.07(S0→S8) 404 1.1799 H-2→L+3(42%) H-1→L(32%) H→L+2(11%) SM315 1.91(S0→S1) 651 0.9497 H→L(63%) H→L+1(16%) H-2→L+2(9%) H-1→L(7%) 3.14(S0→S6) 394 1.5582 H-2→L+2(37%) H→L+1(32%) H-4→L(11%) H-1→L(6%) a
Only orbital percentage >5% are reported; where H=HOMO and L=LUMO.
ACCEPTED MANUSCRIPT Table 2. The EDDMs and CT parameters for all dyes corresponding to the S0→S1 transition. DCT(Å)
F101
0.658
4.853
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F102
0.604
3.932
FSQ102
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0.637
4.541
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0.607
4.171
F105
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4.489
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DCT(Å)
0.719
6.269
0.693
5.937
0.658
5.425
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5.739
SM315
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3.734
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The blue and purple colors symbolizes an decrease and increase in electron density, respectively. The isosurface of electron density is 0.0002 a.u.
ACCEPTED MANUSCRIPT Table 3. The bond length (Å), and adsorption energy (kcal mol-1) of dye-TiO2 complexes calculated by PBE/DNP in the DMol3 module. Ti-O(Å)
Ti-O(Å)
Eads(kcal mol-1)
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Ti-O(Å)
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F101 F102 F103 F104 F105
2.152 2.143 2.141 2.137 2.144
2.130 2.125 2.125 2.119 2.126
-16.4 -0.8 -16.2 -16.8 -15.9
FSQ101 FSQ102 FSQ103 FSQ104 SM315
2.139 2.146 2.130 2.139 2.149
2.121 2.118 2.115 2.124 2.124
-17.2 -18.2 -21.5 -17.1 -15.1
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ACCEPTED MANUSCRIPT Table 4. Calculated electronic properties of the isolated dyes and dye-(TiO2)38 complexes.
(mA cm ) 45.03 44.11 42.00 43.71 43.27 52.14 52.01 51.95 51.96 35.69(18.1)a
Edye (eV)
Edye* (eV)
Ginject (eV)
Greg (eV)
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1.51 1.59 1.56 1.58 1.56 1.32 1.35 1.40 1.38 1.64
-5.32 -5.29 -5.33 -5.31 -5.32 -5.23 -5.22 -5.33 -5.28 -5.33
-3.56 -3.49 -3.51 -3.50 -3.51 -3.63 -3.60 -3.69 -3.64 -3.42
0.44 0.51 0.49 0.50 0.49 0.37 0.40 0.31 0.36 0.58
0.32 0.29 0.33 0.31 0.32 0.23 0.22 0.33 0.28 0.33
0.148 0.151 0.147 0.149 0.148 0.153 0.145 0.150 0.157 0.147
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ACCEPTED MANUSCRIPT Highlights 1. Photophysical properties of porphyrin dyes were systematically studied theoretically. 2. B1 was screened as an excellent π-conjugated bridge candidate for efficient dyes.
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3. FSQ101-104 exhibited enhanced light-harvesting abilities toward the NIR region.
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4. Designed dyes are expected to be promising sensitizers for highly efficient DSSCs.