Mechanofluorochromic and thermochromic properties of simple tetraphenylethylene derivatives with fused fluorine containing 1,4-dioxocane rings

Accepted Manuscript Mechanofluorochromic and thermochromic properties of simple tetraphenylethylene derivatives with fused fluorine containing 1,4-dioxocane rings Hongxiang Wu, Yue Jiang, Yang Ding, Yuying Meng, Zhuo Zeng, Clément Cabanetos, Guofu Zhou, Jinwei Gao, Junming Liu, Jean Roncali PII:

S0143-7208(17)30876-8

DOI:

10.1016/j.dyepig.2017.07.026

Reference:

DYPI 6115

To appear in:

Dyes and Pigments

Received Date: 19 April 2017 Revised Date:

6 July 2017

Accepted Date: 6 July 2017

Please cite this article as: Wu H, Jiang Y, Ding Y, Meng Y, Zeng Z, Cabanetos Clé, Zhou G, Gao J, Liu J, Roncali J, Mechanofluorochromic and thermochromic properties of simple tetraphenylethylene derivatives with fused fluorine containing 1,4-dioxocane rings, Dyes and Pigments (2017), doi: 10.1016/ j.dyepig.2017.07.026. 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.

ACCEPTED MANUSCRIPT

Mechanofluorochromic and Thermochromic Properties of Simple Tetraphenylethylene Derivatives with Fused Fluorine Containing 1,4-Dioxocane Rings

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Hongxiang Wu1&, Yue Jiang2&*, Yang Ding2, Yuying Meng5, Zhuo Zeng1*, Cl é ment Cabanetos 6, Guofu Zhou3, Jinwei Gao2*, Junming Liu2,4, Jean Roncali6

College of Chemistry & Environment, South China Normal University, Guangzhou, 510006,

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1

2

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P. R. China

Institute for Advanced Materials and Guangdong Provincial Key Laboratory of Quantum

Engineering and Quantum Materials, South China Normal University, Guangzhou 510006, P. R. China 3

Electronic Paper Displays Institute, South China Normal University, Guangzhou 510006, P.

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R. China

Laboratory of Solid State Microstructures, Nanjing University, Nanjing 210093, P. R. China

5

Sun Yat-Sen University, School of Chemistry, Guangzhou, 510275, P. R. China

6

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4

Group Linear Conjugated Systems, CNRS Moltech-Anjou, University of Angers, 2 Bd

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Lavoisier, 49045 Angers, France

Corresponding authors:

Y. Jiang, [email protected] Z. Zeng, [email protected] J. Gao, [email protected] Key

words:

TPE,

Tetrafluorobutylenedioxy

Thermalchromism 1

loops,

Mechanofluorochromism,

ACCEPTED MANUSCRIPT Abstract: A series of tetraphenylethylenes (TPE) derivatives in which one or more of the phenyl

rings

have

been

replaced

by

a

fused

fluorine

containing

2,3,4,5-

tetrahydrobenzo[b][1,4]dioxocane unit have been synthesized. The analysis of the photoluminescence emission under application of mechanical grinding and thermal treatment

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show that in addition to the expected aggregation induced emission behaviour observed in solution, these simple modifications of the TPE system confer mechanofluorochromic properties to the corresponding materials. The results of X-ray diffraction and theoretical

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calculations suggest that the introduction of tetrafluorobutylenedioxy “loops” control the balance between weak intermolecular interactions and thus the interconversion between

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“macro” and “micro-aggregates” which is proposed as the basic mechanism for the observed MFC properties.

1. Introduction

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Organic materials endowed with mechanochromic (MC) or mechanofluorochromic (MFC) properties namely properties undergo changes in their absorption or fluorescence emission spectrum in response to the external mechanical stimuli such as hydrostatic pressure,

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grinding or stretching are subject to very significant current interest [1-4]. Over the past few years, various molecular structures with MFC properties have been

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reported including stilbene[5], tetraphenylethylene (TPE) [6, 7, 8], triphenylamine (TPA) [911], anthracene [12, 13] and metal-organic or β-diketone boron complexes[14, 15]. Besides potential applications in various fields, like light emitting diodes[16], memory devices[17], or sensorss[18, 19], the peculiar properties of these materials also pose some interesting fundamental problems related to the packing mode of the molecular unit and especially the kinetics of the mechanically/thermally induced transitions. Hence, intermolecular interactions (Inter-I) represent a key factor that controls the molecular self-assembly and packing arrangements and therefore the chemo-physical and 2

ACCEPTED MANUSCRIPT thermal properties in the solid state. Moreover, previous work suggested that an “appropriate crystallization” capability is a prerequisite for MC materials[20]. Consequently, modulating/tuning the Inter-I through pi-stacking[21], hydrogen bonding[22] or dipole-dipole interaction[23] turns out to be an efficient strategy. Complementarily, we have recently

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demonstrated that the simultaneous presence of lipophilic and hydrophilic parts in push-pull molecules contributes in obtaining metastable materials with MFC behaviour coupled to nonlinear optical properties[24].

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Herein, we report the synthesis of a series of molecules based on tetraphenylethylene (TPE) in which butylenedioxy- and tetrafluorobutylenedioxy- loops have been introduced at

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one or two phenyl groups of the TPE core. The electronic properties of the molecules have been characterized by UV-Vis and fluorescence spectroscopy as well as cyclic voltammetry. Preliminary

evaluations

clearly

demonstrated

that

the

materials

with

tetrafluorobutylenedioxy- loops (C1 and C2) belong to the class of MFC luminogens. The

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thorough investigations of mechano- and thermal- fluorochromic kinetics for the first time has revealed the effect of “micro-” and “macro-” aggregates on the MFC process.

2.1. Synthesis

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2. Results and discussion

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Compounds C1-C4 were synthesized according to the route depicted in Scheme 1. The TPE block of C1 and C3 was built by Suzuki cross-coupling reaction between (2bromoethene-1,1,2-triyl)tribenzene (S1) and 3,4-dimethoxyphenylboronic acid to give (2(3,4-dimethoxyphenyl)ethene-1,1,2-triyl)tribenzene (S2) in 77 % yield. Demethylation of the latter with boron tribromide gave 4-(1,2,2-triphenylvinyl)benzene-1,2-diol (S3) in 81 % yield. Then, the target compounds C1 and C3 were prepared in 93% and 13% yield respectively via Williamson

reaction

between

S3

and

3

2,2,3,3-tetrafluorobutane-1,4-diyl

ACCEPTED MANUSCRIPT bis(trifluoromethanesulfonate) (X) and butane-1,4-diyl bis(4-methylbenzenesulfonate) (Y). It is noteworthy that the moderated yield of C3 can be attributed to the 10,000 times lower reactivity

of

OTs

than

OTf

[25].

In

parallel,

Williamson

reaction

of

(3,4-

dihydroxyphenyl)(phenyl)methanone (D1) with X and Y gave compounds C2 and C4 in 79%

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and 10% yield respectively. Finally, the isomers of C4 are inseparable and 1H NMR and X-

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ray diffraction on single crystal confirmed the conformation of trans-isomer for C2.

Scheme 1. Synthesis of the target compounds C1-C4. i: 5 % mol Pd(PPh3)2Cl2, K3PO4, toluene, 110oC 12h; ii: BBr3, DCM, 25oC, 24 h; iii: CH3CN, K2CO3, 90oC, 12 h; iv: CH3CN,

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K2CO3, 90oC, 72 h; v: Zn, TiCl4, THF, reflux, 12 h.

2.2. Thermal properties

While compounds C1 and C2 were isolated as solids, oily compounds were recovered after purification for C3 and C4. Consequently, the thermal properties of the latter were not further investigated. As shown in Fig. 1, the DSC curve of the as-obtained C1 crystals exhibits a first endothermic peak at 117 oC followed by a small peak at 134 oC.

4

ACCEPTED MANUSCRIPT Endo

0.0 -0.2

DSC [mW/mg]

-0.4 -0.6

C1 C2

-0.8 -1.0 -1.2 -1.4 -1.6 -1.8 100

150

200

250

300

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50

Temperature [oC]

Fig. 1. DSC curve of C1 and C2 with 10 K/min heating rate under nitrogen protection.

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Regarding C2, two peaks were recorded at 141 oC and 223 oC respectively. The absence

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of birefringence under polarized optical microscopy (POM) suggests that the splitting of the peak cannot be attributed to the formation of a liquid crystal phase. A contrario, inverted fluorescence microscopy confirmed that C1 crystals partially melt at ca.110 oC leading to the breaking of large crystals into smaller ones that totally melt at ca.140 oC (Fig. 8b). From this

“micro aggregates”. 2.3. Cyclic voltammetry

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point onwards, large crystals will be referenced as “macro aggregates” and the smaller one as

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Cyclic voltammetry was performed in methylene chloride in the presence of 0.1 M tetrabutylammonium hexafluorophosphate as the supporting electrolyte (Fig. 2). The cyclic

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voltammograms of C1 and C2 present an irreversible oxidation wave with an anodic peak potential (Epa) at 1.36 and 1.35 V and an irreversible reduction wave peaking at Epc = -1.35 and -1.38 V respectively. Comparison the conventional TPE (Epa at 1.40V) shows that the electron donating effect of the butylenedioxy loops on C1 and C2 leads to a small negative shift of ca 50mV in the anodic region.

5

ACCEPTED MANUSCRIPT C1 C2 TPE

-1.0

-0.5

0.0

0.5

1.0

1.5

E/V vs SCE

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-1.5

5µ µA

Fig. 2. Cyclic voltammograms of compounds TPE, C1 and C2. 1mM in 0.1M

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Bu4NPF6/CH2Cl2, scan rate 50mVs-1, Pt working electrodes

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2.4. UV-Vis absorption spectroscopy

The UV-Vis absorption spectra of C1, C2 and TPE were recorded in THF solution and as thin films spin-cast on quartz substrates (Table 1 and Fig. 3). The spectra recorded in solution show a first band in the 230-270 nm region ascribed to the absorption of the phenyl

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rings, followed by a less intense band at λmax 309 nm corresponding to the conjugated TPE system. The introduction of butylenedioxy loops leads to the red shift of the first absorption band from 238 nm for TPE to 240 and 244 nm for C1 and C2 respectively. Furthermore, the

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molar extinction coefficient (ε ) of C1 and C2 is significantly higher than that of TPE, possibly due to the electron donating effect of the alkoxy groups. As generally observed for

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conjugated molecules, the spectra of the solid films present a broadening of the absorption band due to Inter-I. For both solution and solid-state spectra the tetrafluorobutylenedioxyloops produce a small red shift of the first absorption band and have practically no effect on the band at longer wavelength.

6

ACCEPTED MANUSCRIPT 0.5 C1 C2 TPE

Absorbance

0.4 0.3 0.2 0.1

300

400

500

600

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0.0 700

Wavelength (nm)

0.30

0.20

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C1 C2 TPE

0.15 0.10 0.05 0.00 300

400

500

600

700

Wavelength [nm]

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Absorbance [a.u.]

0.25

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Fig. 3. UV-Vis absorption spectra of compound TPE, C1, C2: in THF solution (10-5M) (up); as thin film spin-cast on quartz from THF solution (down).

λF max

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λS max

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Table 1. UV-Vis absorption and cyclic voltammetry data for C1, C2 and TPE.

(nm)

(nm)

εmax

(M-1cm-1)

Epa

Epc

(V vs SCE) (V vs SCE)

TPE 238, 309 244, 325 23000, 14000

1.40

-1.33

240, 309 244, 317 50000, 28000

1.36

-1.35

244, 309 248, 322 44000, 23000

1.35

-1.38

C1 C2

2.5. Aggregation-induced emission (AIE)

7

ACCEPTED MANUSCRIPT Introduced by Tang and co-workers in 2001[26] TPE is probably the most widely employed building block for the synthesis of molecules endowed with aggregation-induced emission (AIE) properties[27,28]. To investigate the effects of the substitution of TPE by the tetrafluorobutylenedioxy loops, UV-Vis absorption and fluorescence emission spectra of TPE,

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C1 and C2 were recorded upon addition of increasing fractions of water in THF solutions. Fig. 4 depicts the UV-Vis profiles recorded in a 10:90 THF/water mixture. It turns out that the high fraction of water induces for all compounds a bathochromic shift of λmax and a

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broadening of the spectra. However, it is worth noting that the reference TPE is characterized by a discernible new shoulder at ca 420 nm which is absent in the spectra of C1 and C2. This

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difference suggests that bare TPE has a stronger propensity to aggregate than its substituted versions.

1.0 0.8 0.6 0.4 0.2

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Normalized Absorbance

1.2

0.0 300

400

500

600

700

Wavelength [nm]

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0.8 0.6 0.4 0.2 0.0

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Normalized Absorbance

1.0

300

400

500

600

700

Wavelength [nm]

Normalized Absorbance

1.0 0.8 0.6 0.4 0.2 0.0

300

400

500

600

700

Wavelength [nm]

8

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Fig. 4. UV-Vis Absorption spectra of TPE (top), C1 (middle) and C2 (bottom). In THF (black) and in 1:9 THF/water (red).

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Photoluminescence responses of C1, C2 and TPE were then analyzed by fluorescence spectroscopy. As depicted in Fig. 5, no fluorescence emission was observed in pure THF for all compounds. However, increasing the volume fraction of water beyond 80% leads to the

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triggering of fluorescence emission with emission maximum at 460 nm for TPE, shifting to

can also exhibit prominent AIE process.

350

400

450

500

550

EP

Wavelength [nm]

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Fluorescence

80% 82% 84% 86% 88% 90%

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471nm for both C1 and C2. These results thus confirm the similarly to TPE since C1 and C2

400

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Fluorescence

80% 82% 84% 86% 88% 90%

450

500

550

Wavelength [nm]

9

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Fluorescence

80% 82% 84% 86% 88% 90%

400

450

500

550

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Wavelength [nm]

Fig. 5. Fluorescence emission spectra of TPE (top), C1 (middle) and C2 (bottom) in THF-

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water mixtures. Concentration: 0.5 mM. Excitation wavelength: 300 nm.

2.6. Calculations

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Molecular optimal geometries of C1 to C4 were calculated by DFT based B3LYP functional with the 6-31G(d,p) basis set using the Gaussian09 software package[29]. The computed structures show no imaginary frequency, thus ensuring energetic minima. In the neutral state, C1 to C4 molecules show the expected representative propeller-like shape of the

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common TPE block. Furthermore, it was also shown that the butylenedioxy loops adopt a chair conformation mainly induced by the number of atoms involved in the cycles (Fig. S1) [30]. Then, to gain further insight into the stacking patterns, the Materials Studio [31]

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polymorph predictor module was used. Through the calculation of the total energy between two adjacent molecules, packing styles with the top 10 minimal energy are listed in Table S1

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for both compounds. First regarding C2, top 10 lowest total energy ranging from 102.7 to 103.0 eV display minor difference (0.3eV) and each of their corresponding packing styles presents weak F…F interaction (2.850 Å to 2.866 Å) of butylenedioxy loops at both sides. For instance, the most stable packing style is illustrated in Fig. 6 (c). In the case of C1, a significantly larger energy difference of 1.3eV was estimated from 77.9eV of lowest total energy jump to next 79.2 eV. The calculated most stable packing mode of C1 shows interactions between the electronrich TPE and the electron-deficient tetrafluoroethyl without reasonable CH…F interactions 10

ACCEPTED MANUSCRIPT (Fig. 6a and Table S1 C1 P-1-1) while the second stable packing results from the CH…F interaction characterized by a distance of 2.659 Å (Table S1 C1 P-1-2 and Fig. 6b). Thus regarding C3 and C4, the absence of the intermolecular interactions associated with fluorine atoms, provides a further support to understand their oily state at room temperature. The

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results from these calculations are consistent with the more prominent two-step thermal behavior of C1 vs C2 due to the larger Inter-I associated with the presence of two

EP

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tetrafluorobutylenedioxy loops in C2.

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Fig. 6. (a)-(c) Calculation result: (a) C1 packing with the minimum total energy. (b) C1 packing with the second minimum total energy. (c) C2 packing with the minimum total energy. (d)-(f) Photograph of C2 single crystals: (d) structure of C2. (e) Vertical CH…F interaction of C2. (f) In-plane CH…F interaction of C2.

2.7. Single Crystallography Used as the reference structure, the basic TPE presents two sets of benzene rings around the central C=C bond, with dihedral angles of 55o and 85o between phenyl rings fixed on 11

ACCEPTED MANUSCRIPT different alkene carbons and 79 o and 74o between phenyl rings attached on the same alkene carbon[32] (Fig. 7). Regarding the butylenedioxy functionalized molecules, only single crystals of C2 were obtained by slow evaporation of dichloromethane solutions. It turns out that the dihedral angles between phenyl rings borne by the same alkene carbons are of ca. 89o

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while those on different alkene carbons are of ca. 49 o and 68 o respectively (Fig. 7). As might be expected, introduction of fluorine substituted butylenedioxy loops clearly increases the intramolecular propelling level. Moreover, the crystal structure also reveals that the

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butylenedioxy loops adopt a trans- chair conformation with C12-O2-C17 bond angle of 115.22o that does not inhibit the packing of the TPE core. More interestingly, two kinds of

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H…F interactions, ie, F3…H2 and F4…H17B with distance of 2.624 Å and 2.589 Å respectively were monitored (Fig. 6e-f). It is noteworthy that these two distances are shorter than the sum of the Van der Waals Radius of hydrogen and fluorine (ie 2.67 Å). These weak Inter-Is are consistent with the much higher melting point of C1 and C2 compared to C3 and

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C4.

Fig. 7. Crystal structures of TPE (Left) and C2 (Right).

2.8. MFC It has been shown that due to its high propensity to crystallize, bare TPE does not exhibit MFC behaviour [33,34]. On the other hand, previous work has shown that the modification of the TPE core by partial rigidification[33] or by introduction of various

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ACCEPTED MANUSCRIPT substituents such as dimethylamino [35], methoxy[36] led to materials presenting MFC properties. Samples of C1 and C2, as polycrystalline powders are re-crystallized from DCM solution. Pristine and ground crystals were compared to each other

and

exposed

to

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thermal treatment at different temperatures. Images recorded under monochromatic illumination at 365 nm by inverted fluorescence microscopy are depicted in Fig. 8 and 9. Upon grinding, the fluorescence of C1 changes from purple blue (Fig. 8a) to sky blue

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(Fig. 8c) which corresponds to a red shift from 415 nm to 448 nm of the fluorescence emission maximum (λem). Thermal annealing of the pristine crystals at 110°C produces

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partial melting, in agreement with DSC data (Fig. 1), while the color of fluorescence turns to sky blue (λem= 453 nm) with an emission spectrum quite close to that of the ground crystals (Fig. 8b and c). On the other hand, heating the ground pristine crystal at 110°C produces the reverse effect with a hypsochromic shift of λem to 435 nm (Fig. 8d). Further heating, up to 140 o

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C, induces a total melting of both the pristine and the ground samples.

Fig. 8. Left: Pics of C1 powder recorded at various temperatures under inverted fluorescence microscopy (excitation wavelength 365nm). Right: fluorescence emission spectra of C1 (excitation wavelength 300 nm) “P” stands for “pristine crystals” and “G” for “ground powders”.

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Fig. 9. Left: Pics of C2 powder recorded at various temperatures under inverted fluorescence

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microscopy (excitation wavelength 365nm). Right: fluorescence emission spectra of C1 (excitation wavelength 300 nm) “P” stands for “pristine crystals” and “G” for “ground powders”.

For C2, the maximum of the fluorescence emission λem shifts bathochromically from

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purple blue (419 nm) to sky blue (433 nm) (Fig. 9a and d) under mechanical stimulation. Upon slow heating the pristine crystals begin to melt at 120oC while λem shifts to 458 nm (Fig. 9b). On the other hand, a 5 min thermal treatment of the ground sample at 110 oC leads

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to a hypsochromic shift of λem from 433 nm back to 419 nm (Fig. 9d) and the sample exhibits

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again the purple blueish fluorescence characteristic of the pristine sample at room temperature (Fig. 9a). However, keeping the sample at 110°C for a longer time (30 min) leads to a stabilized emission spectrum similar to that of the ground samples recorded at room temperature with λem = 435 nm, (Fig. 9c and 8e).

2.9. Powder X-ray Diffraction These various mechanically and thermally induced transformations have been followed using powder X-ray diffraction (XRD) measurements. The pristine crystals of C1 present 14

ACCEPTED MANUSCRIPT multiple peaks in the range of 10-30 degree (Fig. 10). Grinding of the crystals produces the disappearance of these peaks whereas a subsequently TA partially restores the initial signals. The XRD curve of the pristine C2 also presents multiple peaks between 0 and 40°, but in the diagram of ground C2, the intensity of the peak at 17o increases while that of the other peaks

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decreases. A 5 min TA at 110°C restores some signals (e.g. 10.7o and 14.7o) common to the pristine sample while after 30min TA at 110°C only the strong peak at 17o observed on the ground samples remains, which suggests that a prolonged TA induces a modification of the

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Pristine Ground After TA-5min After TA-30min

Intensity

Intensity

Pristine Ground After TA

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crystalline state of C2.

10

15

20

2θ θ /ο

25

30

35

10

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5

15

20

25

30

35

40

2θ θ /o

2.10. Discussion

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Fig. 10. Powder XRD patterns of C1 (left) and C2 (right) in different states.

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The foregoing results show that introducing of tetrafluorobutylenedioxy loops on one or two of the phenyl rings of TPE can effectively confer MFC properties on the resulting materials. Based on the thermal and luminescent properties of the materials it can be proposed that the application of external mechanical force to the pristine “macro aggregates” of C1 leads to their conversion into “micro aggregates” associated with a change of the fluorescence emission from purple blue to sky blue. Application of a subsequent TA at 110o C to the ground samples rebuilt the purple blue “macro aggregates”. Although a similar behavior is observed for C2, a prolonged TA at 110° leads to a change of the purple blue state to sky blue 15

ACCEPTED MANUSCRIPT fluorescent crystals. These various results show that 110o C represents a key temperature for the metastable C1 and C2. As suggested by single crystal XRD and calculations, intermolecular H…F and F…F interactions play a fundamental role in both the molecular packing and the sensitivity of the

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materials to mechanical and thermal stimulations. Thus, it can be proposed that mechanical forces or heat essentially destroy the “macro order” controlled by weak H…F interactions whereas the “micro order” controlled by relatively strong interactions, such as attraction

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between electron-rich TPE block and electron-deficient tetrafluoroethylene block for C1 and

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the stronger H…F interaction for C2 are less affected by these external stimulations.

3. Conclusion

To summarize tetraphenylethylenes derivatized with one or two tetrafluorobutylene loops have been synthesized. The analysis of the photoluminescence emission under

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application of mechanical grinding and thermal treatment show that in addition to the expected AIE behavior observed in solution, these simple modifications of the TPE system confer MFC properties to the corresponding materials. The results of X-ray diffraction and

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theoretical calculations suggest that the introduction of tetrafluorobutylenedioxy loops controls the balance between weak intermolecular interactions and thus the interconversion

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between “macro” and “micro-aggregates” which is proposed as the basic mechanism for the observed MFC properties.

[CCDC 1524482 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.]

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ACCEPTED MANUSCRIPT Supporting Information Supporting Information is available from the Wiley Online Library or from the author.

Acknowledgements

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We thank the financial support from National Natural Science Foundation of China (21272080, 51571094), China Postdoctoral Science Foundation (2016M590795), National Key Research Program of China (2016YFA0201002), Guangdong Province Foundation

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((2016KCXTD009, 2014B090915005, and 2016A010101023), and Guangdong Innovative Research Team Program (2011D039). We also thank the support from the Joint International

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Research Laboratory of Optical Information. Hongxiang Wu and Yue Jiang contributed equally to this work.

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Zou, S. X.-A. Zhang, J. Am. Chem. Soc. 2015, 137, 931. [19] H. Lu, Y. Zheng, X. Zhao, L. Wang, S. Ma, X. Han, B. Xu, W. Tian, H. Gao, Angew.

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Chem. Int. Ed. 2016, 55, 155. [20] Y. Q. Dong, J. W. Y. Lam, B. Z. Tang, J. Phys. Chem. Lett. 2015, 6, 3429. [21] Q. Song, Y. Wang, C. Hu, Y. Zhang, J. Sun, K. Wang, C. Zhang, New J. Chem. 2015, 39, 659. [22] Y. Sagara, T. Mutai, I. Yoshikawa, K. Araki, J. Am. Chem. Soc. 2007, 129, 1520. [23] J. Wu, Y. Cheng, J. Lan, D. Wu, S. Qian, L. Yan, Z. He, X. Li, K. Wang, B. Zou, J. You, J. Am. Chem. Soc. 2016, 138 39, 12803.

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ACCEPTED MANUSCRIPT [24] Y. Jiang, D. Gindre, M. Allain; P. Liu, C. Cabanetos, J. Roncali, Adv. Mater. 2015, 27, 4285. [25] M. Smith, J. March, March's Advanced Organic Chemistry: Reactions, Mechanisms, and Structure, Sixth Edition, 2006, 501-502.

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[26] J. Luo, Z. Xie, J. W. Y. Lam, L. Cheng, H. Chen, C. Qiu, H. S. Kwok, X. Zhan, Y. Liu, D. Zhu, B. Z. Tang, Chem. Commun. 2001, 1740.

[27] Y. Hong, J. W. Y. Lam, B. Z. Tang, Chem. Soc. Rev. 2011, 40, 5361.

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[28] Z. Zhao, J. W. Y. Lam, B. Z. Tang, J. Mater. Chem. 2012, 22, 23726.

[29] M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria,M. A. Robb, G. Scalmani, J.

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R. Cheeseman, V. Barone,B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato,X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng,J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda,J. Hasegawa, M. Ishida, T. Nakajima, O. Kitao, Y. Honda,H. Nakai, T. Vreven, J. A. Montgomery, J. E. Peralta,F. Ogliaro, M. Bearpark, J.

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J. Heyd, E. Brothers,K. N. Kudin, V. N. Staroverov, R. Kobayashi, J. Normand,K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar,J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene,J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo,R.

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Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin,R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin,K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador,J. J.

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Dannenberg, S. Dapprich, A. D. Daniels, O. Farkas,J. B. Foresman, J. V. Ortiz, J. Cioslowski and D. J. Fox, Gaussian 09W Revision B.02. [30] Z. Zeng, J-W Zhong, H Wang, J. Wang, Acta Crystallogr E 2010, 66, o1137. [31] Accelrys Inc., Accelrys Materials Studio, San Diego, 2005 [32] I. Ino, L. P. Wu, M. Munakata, Y. Kuroda-Sowa, M. Maekawa, Y. Suenaga, R. Sakai, Inorg. Chem. 2000, 39, 5430.

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ACCEPTED MANUSCRIPT [33] J. Shi, N. Chang, C. Li, J. Mei, C. Deng, X. Luo, Z. Liu, Z. Bo, Y. Q. Dong, B. Z. Tang, Chem. Commun. 2012, 48, 10675. [34] Y. Wang, I. Zhang, B. Yu, X. Fang, X. Su, Y-M. Zhang, T. Zhang, B. Yang, M. Li, S. X-A. Zhang, J. Mater. Chem. C 2015, 3, 12328.

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[35] Q. Qi, J. Zhang, B. Xu, B. Li, S. X-A. Zhang, W. J. Tian, Phys. Chem. C 2013, 117, 24997.

[36] C. Li, X. Luo, W. Zhao, C. Li, Z. Liu, Z. Bo, Y. Dong, Y. Q. Dong, B. Z. Tang,

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New J. Chem. 2013, 37, 1696.

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Supporting Information Mechanofluorochromic and Thermochromic Properties of Simple Tetraphenylethylene Derivatives with Fused Fluorine Containing

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1,4-Dioxocane Rings Hongxiang Wu1&, Yue Jiang2&*, Yang Ding2, Yuying Meng5, Zhuo Zeng1*, Clément Cabanetos 6, Guofu Zhou3, Jinwei Gao2*, Jun-Ming Liu2,4, Jean Roncali6 1

College of Chemistry & Environment, South China Normal University, Guangzhou, Guangdong 510006, China

2

Institute for Advanced Materials and Guangdong Provincial Key Laboratory of Quantum Engineering and

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Quantum Materials, South China Normal University, Guangzhou 510006, P. R. China

Electronic Paper Displays Institute, South China Normal University, Guangzhou 510006, P. R. China

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Laboratory of Solid State Microstructures, Nanjing University, Nanjing 210093, P. R. China

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Sun Yat-Sen University, School of Chemistry, Guangzhou, 510275, P. R. China

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. Moltech-Anjou, CNRS, University of Angers

Corresponding authors: Y. Jiang, [email protected] Z. Zeng, [email protected]

Content: 1, General information

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J Gao, [email protected]

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3, Calculation 4, Single crystal

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2, Synthesis and NMR spectra

1, General Information

All reagents and chemicals from commercial sources were used without further purification. Reactionswere carried out under argon atmosphere unless otherwise stated. Solvents were dried and purifiedusing standard techniques. Flash chromatography was performed with analytical-grade solvents using QingDao silica gel (technicalgrade, pore size 60 Å, 200-300 mesh particle size). Reactions were monitored by TLC on Merck silica gel 60 F254 plates visualized by UV lump at 254 nm. Compounds were detected by UV irradiation (YuHua). NMR spectra were recorded with Varian Unity AS 400 MHz (1H, 400 MHz and 13C, 100 MHz). Chemical shifts are given in ppm relative to TMS and coupling constants J in Hz. High Resolution Mass was performed on Thermo spectrometer MAT95XP. Thermogravimetric 21

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analyses (TGA) and differentialScanning Calorimetry (DSC) were carried out under dry nitrogen gas flow with a 10oC min-1 heating rate on Mettler Toledo TGA 2 and a Mettler Toledo DSC 1 respectively. Single crystaldiffractions were recorded with single crystal diffractometer KAPPA CCD (Bruker-Nonius) equippedwith liquid nitrogen cooling system (Oxford) and graphite monochromator utilizing MoK radiation (λ = 0.71073 Å). Single crystals for X-ray diffraction were prepared by slow evaporation of DCM solutions. UV-Vis spectra were recorded with a PerkinElmer LAMBDA 950 UV/Vis/NIR Spectrophotometer. Solution was with dichloromethane and film was spun-cast on quartz from dichloromethane solution with 10mg/mL concentration. Fluorescence spectroscopy was recorded on HITACHI F-4600 with excitation wavelength of 300nm. Cyclic voltammetry was performed in 0.10 M Bu4NPF6/CH2Cl2 (HPLC grade). Solutions were degassed by nitrogen bubbling prior to each experiment. Experiments were carried out in a one-compartment cell equipped with platinum electrodes and a saturated calomel reference electrode (SCE) using a ZAHNER PP211potentiostat. The crystallinity of powder was checked using the X-ray diffraction (XRD) (PANalytical X’Pert PRO diffractometer) with the Cu-K radiation at room temperature and inverted fluorescence microscopy on OLYMPUS IX73 with Andor iXon Ultra High Speed EMCCD Camera. UV irradiation is from the portable UV lamp with 365nm. Single crystal X-ray diffraction was carried out on a Bruker SMART APEX II X-ray diffracter. 2, Synthesis:

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5 % mol Pd(PPh3)2Cl2

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K3PO4, toluene, 110oC 12h O O

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An oven-dried round-bottomed flask (50 mL) equipped with a stir bar was charged with 1bromo-1,2,2-triphenylethene (5 mmol, 1.0 equiv), toluene (typically, 15 mL), 3,4dimethoxyphenylboronic acid (5 mmol, 1.0 equiv) and K3PO4 (5 mmol, 1.0 equiv). Pd(PPh3)2Cl2 (5 % mol) was added to the reaction mixture with vigorous stirring at 110 oC, and maintained the temperature at 110 oC for 12 h. After the indicated time, the reaction mixture was concentrated. The obtained residue was purified by column chromatography (Petroleum ether/EtOAc=10/1) to afford1-(1-(3,4-dimethoxyphenyl)-2,21 diphenylvinyl)benzene (S2)(1.51g, 77.1%). H NMR (400 MHz, CDCl3) δ 7.18 – 6.97 (m, 15H), 6.65 – 6.61 (m, 1H), 6.54 (td, J = 4.4, 2.0 Hz, 2H), 3.81 (s, 3H), 3.47 (s, 3H).13C NMR (100 MHz, CDCl3) δ 147.75, 147.53, 144.20, 143.82, 143.68, 140.66, 140.12, 136.13, 131.41, 131.31, 131.13, 127.82, 127.58, 127.57, 126.41, 126.29, 126.24, 123.94, 115.04, 110.14, 55.63, 55.50. HRMS (EI) m/z: Calcd for C28H24O2: 392.1776 Found 392.1771.

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An oven-dried round-bottomed flask (50 mL) equipped with a stir bar was charged with CH2Cl2 (typically, 20 mL), 1-(1-(3,4-dimethoxyphenyl)-2,2-diphenylvinyl)benzene (3 mmol, 1.0 equiv, 1.18 g), BBr3 (9 mmol, 3.0 equiv, 2.25 g)was added dropwise to the reaction mixture with vigorous stirring at 0oC and maintained the temperature at 25 oCfor 24 h. the reaction mixture was poured into 80 mL ice-water and extracted with DCM three times (20 mL every time). The organic layer was combined and washed with brine three times (30 mL every time), dried, and concentrated. After the solvent was removed, the crude product was purified by silica gel column chromatography to give 4-(1,2,2-triphenylvinyl)benzene-1,2diol(S3) (0.88 g, 81.2%).1H NMR (400 MHz, CDCl3) δ 7.17 – 6.93 (m, 15H), 6.60 (d, J = 8.2 Hz, 1H), 6.54 – 6.46 (m, 2H), 5.13 (s, 1H), 4.96 (s, 1H).13C NMR (100 MHz, CDCl3) δ 150.59, 148.01, 144.02, 143.87, 143.80, 142.62, 142.55, 142.50, 140.41, 140.21, 131.33, 131.25, 127.70, 127.59, 126.38, 126.30, 126.26, 124.65, 118.42, 114.61, 60.51, 53.41, 21.03, 14.18. -cESI-MS Calcd for C26H20O2: 364.1463 Found [M-H] 363.1386.

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An oven-dried round-bottomed flask (100 mL) equipped with a stir bar was charged with CH3CN (typically, 30 mL), 4-(1,2,2-triphenylvinyl)benzene-1,2-diol (3 mmol, 1.0 equiv, 1.10 g), 2,2,3,3-tetrafluorobutane-1,4-diyl bis(trifluoromethanesulfonate) (3 mmol, 1.0 equiv, 1.28 g), K2CO3 (6 mmol, 2.0 equiv, 0.83 g) The reaction mixture was vigorous stirring at 90 oC for 12 h. After the solvent was removed, the crude product was purified by silica gel column chromatography to give product C1 (1.37g, 93.2%). The product was dissolved in DCM, and the desired crystalline product was obtained via slowly evaporated of the solution. 1H NMR (400 MHz, CDCl3) δ 7.19 – 7.07 (m, 9H), 7.06 – 6.97 (m, 6H), 6.82 – 6.76 (m, 1H), 6.72 (dt, J = 8.2, 1.9 Hz, 2H), 4.47 (t, J = 10.5 Hz, 2H), 4.24 (t, J = 10.5 Hz, 2H). 13C NMR (101 MHz, CDCl3) δ 147.42, 147.03, 143.46, 143.25, 143.02, 141.53, 140.74, 139.27, 131.20, 131.19, 131.17, 128.29, 127.84, 127.78, 127.66, 126.65, 126.61, 126.56, 125.41, 121.09, 70.07(t, 2JC-F = 32 Hz), 69.77 (t, 2JC-F = 35 Hz). 19F NMR (376 MHz, CDCl3) δ-122.21, -122.3. HRMS (EI) m/z: [M]+ Calcd for C30H22F4O2: 490.1556 Found 490.1567. O OH OH

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An oven-dried round-bottomed flask (100 mL) equipped with a stir bar was charged with CH3CN (typically, 30 mL), (3,4-dihydroxyphenyl) (phenyl)methanone (3 mmol, 1.0 equiv, 0.64 g), 2,2,3,3-tetrafluorobutane-1,4-diyl bis(trifluoromethanesulfonate) (3 mmol, 1.0 equiv, 1.28 g), K2CO3 (6 mmol, 2.0 equiv, 0.83 g) The reaction mixture was vigorous stirring at 90 o C for 12 h. After the solvent was removed, the crude product was purified by silica gel column chromatography to give the target product D2 (0.97g, 95.1%).1H NMR (400 MHz, CDCl3) δ 7.76 (d, J = 7.2 Hz, 2H), 7.64 – 7.45 (m, 5H), 7.14 (d, J = 8.4 Hz, 1H), 4.65 (t, J = 10.9 Hz, 2H), 4.48 (t, J = 10.9 Hz, 2H).19F NMR (376 MHz, CDCl3) δ-123.11, -123.49. 13C NMR (101 MHz, cdcl3) δ 194.60, 151.93, 147.39, 137.23, 134.08, 132.53, 129.79, 128.37,

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127.66, 125.08, 121.84, 70.16(t, 2JC-F = 32 Hz), 69.43(t, 2JC-F = 30 Hz). HRMS (EI) m/z: Calcd for C17H12F4O3: 340.0723 Found 340.0727.

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An oven-dried round-bottomed flask (50 mL) equipped with a stir bar was charged with THF (typically, 25mL), D2 (3 mmol, 1.0 equiv), Zn powder (9 mmol, 3.0 equiv). TiCl4 (4.5 mmol, 1.5 equiv) was added dropwise to the reaction mixture with vigorous stirring at 0 oC. Next, maintained the temperature at 70 oC for 12 h. After the solvent was removed, the crude product was purified by silica gel column chromatography to give product C2 (0.77 g, 79.3%). The product was dissolved in DCM, and the desired crystalline product was obtained via slowly evaporated of the solution.1H NMR (400 MHz, CDCl3) δ 7.11 (dd, J = 10.2, 7.1 Hz, 6H), 7.00 – 6.92 (m, 4H), 6.81 (d, J = 8.3 Hz, 2H), 6.69 (dd, J = 12.1, 3.8 Hz, 4H), 4.46 (t, J = 10.4 Hz, 4H), 4.33 (t, J = 10.4 Hz, 4H).13C NMR (100 MHz, CDCl3) δ 147.70, 147.11, 142.73, 140.64, 139.97, 131.09, 128.03, 127.83, 126.88, 125.01, 121.52, 70.05(t, 2JC-F = 35 Hz), 69.67(t, 2JC-F = 32 Hz) 19F NMR (376 MHz, CDCl3) δ -122.45, -122.49. HRMS (EI) m/z: [M+NH4]+ Calcd for C34H24F8O4: 666.1885; Found 666.1882.

OH

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S3

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An oven-dried round-bottomed flask (100 mL) equipped with a stir bar was charged with CH3CN (typically, 30 mL), (3,4-dihydroxyphenyl) (phenyl)methanone (3 mmol, 1.0 equiv, 0.64 g), S3 (3 mmol, 1.0 equiv, 1.19 g), K2CO3 (6 mmol, 2.0 equiv, 0.83 g) The reaction mixture was vigorous stirring at 90 oC for 12 h. After the solvent was removed, the crude product was purified by silica gel column chromatography to give product D3 (0.12g, 15.6%).1H NMR (400 MHz, CDCl3) δ 7.76 (d, J = 7.2 Hz, 2H), 7.60 – 7.43 (m, 5H), 7.00 (d, J = 8.4 Hz, 1H), 4.56 (t, J = 5.6 Hz, 2H), 4.31 – 4.22 (m, 2H), 2.00 (dt, J = 11.5, 5.8 Hz, 2H), 1.90 – 1.82 (m, 2H).13C NMR (100 MHz, CDCl3) δ 195.15, 155.24, 146.87, 138.07, 132.15, 131.92, 129.74, 128.21, 126.89, 126.37, 120.87, 74.22, 71.19, 28.07, 25.08. HRMS (EI) m/z: Calcd for C17H16O3: 268.1099 Found 268.1102. 24

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An oven-dried round-bottomed flask (100 mL) equipped with a stir bar was charged with CH3CN (typically, 30 mL), 4-(1,2,2-triphenylvinyl) benzene-1,2-diol (3 mmol, 1.0 equiv, 1.10 g), S1 (3 mmol, 1.0 equiv, 1.19 g), K2CO3 (6 mmol, 2.0 equiv, 0.83 g) The reaction mixture was vigorous stirring at 90 oC for 12 h. After the solvent was removed, the crude product was purified by silica gel column chromatography to give product C3 (0.16 g, 13.1%). 1H NMR (400 MHz, cdcl3) δ 7.19 – 6.91 (m, 15H), 6.66 (d, J = 8.3 Hz, 1H), 6.56 (ddd, J = 8.1, 4.0, 1.9 Hz, 2H), 3.96 (dd, J = 14.2, 8.4 Hz, 2H), 3.64 (dd, J = 12.6, 6.8 Hz, 2H), 1.97 – 1.72 (m, 4H).13C NMR (100 MHz, CDCl3) δ 144.18, 143.86, 143.66, 140.69, 140.15, 137.06, 137.01, 131.40, 131.33, 131.20, 127.74, 127.58, 126.38, 126.24, 124.86, 124.80, 119.72, 119.46, 114.74, 114.56, 26.48, 26.35, 26.24, 26.17. HRMS (EI) m/z: [M]+ Calcd for C30H26O2: 418.1933; Found: 418.1934.

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3, Calculation:

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A single molecule was optimized by the DMol3 module and the electrostatic potential charges of all atoms were obtained. Then the crystal structure prediction1, space groups restricted to P12, was carried out by employing the PBE functional and the Dreiding force field3, which were considered as the most valuable force field to predict the crystal structure

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ACCEPTED MANUSCRIPT Figure S1. C1 to C4 Structure optimization by DFT Table S1 Stacking patterns with the top 10 minimal total energy predicted by polymorph predictor.

Reference:

Length a 9.15 14.65 14.30 17.87 19.31 5.97 12.44 12.18 12.82 12.68 10.78 13.48 11.75 13.51 10.83 13.50 10.71 18.21 28.80 19.79

Length b 11.60 14.17 8.98 5.93 5.93 13.57 8.94 14.34 9.79 13.04 13.47 10.79 13.47 10.75 13.43 10.71 11.66 13.45 10.66 11.23

Length c 12.36 8.29 12.74 13.57 12.44 18.08 12.43 8.97 11.61 9.78 13.43 13.40 20.88 13.88 13.46 13.47 13.97 11.92 14.04 7.00

Angle alpha 89.20 118.24 121.88 113.67 92.23 73.24 116.42 109.64 105.51 120.67 75.33 68.96 113.76 115.48 75.20 69.23 100.17 129.78 114.13 89.97

Angle beta 72.66 101.16 119.40 101.46 74.47 97.17 95.74 84.87 106.43 111.92 111.08 75.25 105.62 79.92 56.65 104.61 114.40 133.04 95.76 86.77

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Total energy 77.92 79.24 79.39 79.53 79.53 79.68 79.73 79.74 79.76 79.76 102.72 102.73 102.73 102.75 102.78 102.82 102.86 102.94 103.01 103.04

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Cell volume 1.21E+03 1.25E+03 1.21E+03 1.23E+03 1.23E+03 1.24E+03 1.23E+03 1.23E+03 1.27E+03 1.26E+03 1.52E+03 1.52E+03 1.52E+03 1.52E+03 1.52E+03 1.52E+03 1.52E+03 1.53E+03 1.52E+03 1.54E+03

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C1 P-1 - 1 C1 P-1 - 2 C1 P-1 - 3 C1 P-1 - 4 C1 P-1 - 5 C1 P-1 - 6 C1 P-1 - 7 C1 P-1 - 8 C1 P-1 - 9 C1 P-1 - 10 C2 P-1 - 1 C2 P-1 - 2 C2 P-1 - 3 C2 P-1 - 4 C2 P-1 - 5 C2 P-1 - 6 C2 P-1 - 7 C2 P-1 - 8 C2 P-1 - 9 C2 P-1 - 10

Space group P-1 P-1 P-1 P-1 P-1 P-1 P-1 P-1 P-1 P-1 P-1 P-1 P-1 P-1 P-1 P-1 P-1 P-1 P-1 P-1

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1 Sokolov, A. N.; Atahan-Evrenk S.; Mondal R.; Akkerman H. B.; Sánchez-Carrera R. S.; Granados-Focil S.; Schrier J.; Mannsfeld S.C.B.; Zoombelt A. P.; Bao Z.; AspuruGuzik A. Nat. Commun. 2011, 2, 437. 2 Zhang B.; Kan Y.-H.; Geng Y.; Duan Y.-A.; Li H.-B.; Hua J.; Su Z.-M. Org. Electron. physics, Mater. Appl.2013, 14, 1359. 3 Mayo S. L.; Olafson B. D.; Goddard W. A. J. Phys. Chem., 1990, 94, 8897. 4, single crystal

Table 1. Crystal data and structure refinement for cd16512. Identification code cd16512 Empirical formula C34 H24 F8 O4 Formula weight 648.53 Temperature 293(2) K Wavelength 0.71073 Å Crystal system Monoclinic 36

Angle gamma 75.27 112.12 70.78 101.89 64.93 66.20 90.22 122.94 66.71 69.34 123.12 56.96 130.01 122.98 68.74 123.04 73.75 76.59 142.68 80.90

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Space group C 2/c Unit cell dimensions a = 19.584(4) Å = 90°. = 108.571(4)°. b = 5.5424(12) Å c = 27.656(6) Å  = 90°. Volume 2845.6(11) Å3 Z 4 Density (calculated) 1.514 Mg/m3 Absorption coefficient 0.133 mm-1 F(000) 1328 Crystal size 0.220 x 0.170 x 0.130 mm3 Theta range for data collection 2.194 to 25.499°. Index ranges -19<=h<=23, -6<=k<=6, -33<=l<=31 Reflections collected 7736 Independent reflections 2661 [R(int) = 0.0335] Completeness to theta = 25.242° 99.9 % Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.7456 and 0.6419 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 2661 / 0 / 209 Goodness-of-fit on F2 1.038 Final R indices [I>2sigma(I)] R1 = 0.0401, wR2 = 0.1034 R indices (all data) R1 = 0.0503, wR2 = 0.1097 Extinction coefficient 0.0035(5) Largest diff. peak and hole 0.197 and -0.186 e.Å-3

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Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for cd16512. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. ___________________________________________________________________________ _____ x y z U(eq) ___________________________________________________________________________ _____ F(1) 1934(1) 4158(3) 428(1) 91(1) F(2) 2100(1) 8022(3) 391(1) 94(1) F(3) 729(1) 6596(3) 69(1) 81(1) F(4) 1014(1) 9021(2) 722(1) 68(1) O(1) 2326(1) 8121(2) 1506(1) 49(1) O(2) 1197(1) 4421(2) 1344(1) 42(1) C(1) 456(1) 10285(3) 3464(1) 47(1) C(2) 714(1) 10343(4) 3990(1) 56(1) C(3) 1171(1) 8590(4) 4255(1) 55(1) C(4) 1384(1) 6803(4) 3994(1) 56(1) C(5) 1140(1) 6758(3) 3467(1) 46(1) 37

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C(6) 658(1) 8472(3) 3194(1) 36(1) C(7) 359(1) 8346(3) 2625(1) 37(1) C(8) 895(1) 8177(3) 2348(1) 36(1) C(9) 1460(1) 9816(3) 2430(1) 40(1) C(10) 1922(1) 9712(3) 2145(1) 41(1) C(11) 1848(1) 7958(3) 1776(1) 36(1) C(12) 1297(1) 6287(3) 1698(1) 35(1) C(13) 841(1) 6396(3) 1987(1) 37(1) C(14) 2408(1) 6186(4) 1194(1) 51(1) C(15) 1889(1) 6303(4) 656(1) 56(1) C(16) 1090(1) 6720(4) 577(1) 50(1) C(17) 745(1) 4982(3) 844(1) 47(1) ___________________________________________________________________________ _____ Table 3. Bond lengths [Å] and angles [°] for cd16512. _____________________________________________________ F(1)-C(15) 1.362(2) F(2)-C(15) 1.346(2) F(3)-C(16) 1.3588(19) F(4)-C(16) 1.359(2) O(1)-C(11) 1.3753(18) O(1)-C(14) 1.416(2) O(2)-C(12) 1.3952(19) O(2)-C(17) 1.417(2) C(1)-C(2) 1.380(2) C(1)-C(6) 1.383(2) C(1)-H(1) 0.9300 C(2)-C(3) 1.366(3) C(2)-H(2) 0.9300 C(3)-C(4) 1.367(3) C(3)-H(3) 0.9300 C(4)-C(5) 1.384(3) C(4)-H(4) 0.9300 C(5)-C(6) 1.382(2) C(5)-H(5) 0.9300 C(6)-C(7) 1.496(2) C(7)-C(7)#1 1.355(3) C(7)-C(8) 1.487(2) C(8)-C(13) 1.384(2) C(8)-C(9) 1.393(2) C(9)-C(10) 1.377(2) C(9)-H(9) 0.9300 C(10)-C(11) 1.382(2) C(10)-H(10) 0.9300 38

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120.69(14) 115.22(13) 120.99(17) 119.5 119.5 120.47(18) 119.8 119.8 119.36(16) 120.3 120.3 120.57(18) 119.7 119.7 120.64(17) 119.7 119.7 117.91(15) 120.81(15) 121.27(15) 121.76(17) 122.07(18) 116.16(13) 117.18(14) 120.80(14) 122.00(14) 120.81(15) 119.6 119.6 121.17(15) 119.4 119.4 115.20(14)

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C(11)-O(1)-C(14) C(12)-O(2)-C(17) C(2)-C(1)-C(6) C(2)-C(1)-H(1) C(6)-C(1)-H(1) C(3)-C(2)-C(1) C(3)-C(2)-H(2) C(1)-C(2)-H(2) C(2)-C(3)-C(4) C(2)-C(3)-H(3) C(4)-C(3)-H(3) C(3)-C(4)-C(5) C(3)-C(4)-H(4) C(5)-C(4)-H(4) C(6)-C(5)-C(4) C(6)-C(5)-H(5) C(4)-C(5)-H(5) C(5)-C(6)-C(1) C(5)-C(6)-C(7) C(1)-C(6)-C(7) C(7)#1-C(7)-C(8) C(7)#1-C(7)-C(6) C(8)-C(7)-C(6) C(13)-C(8)-C(9) C(13)-C(8)-C(7) C(9)-C(8)-C(7) C(10)-C(9)-C(8) C(10)-C(9)-H(9) C(8)-C(9)-H(9) C(9)-C(10)-C(11) C(9)-C(10)-H(10) C(11)-C(10)-H(10) O(1)-C(11)-C(10)

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C(11)-C(12) 1.387(2) C(12)-C(13) 1.375(2) C(13)-H(13) 0.9300 C(14)-C(15) 1.512(3) C(14)-H(14A) 0.9700 C(14)-H(14B) 0.9700 C(15)-C(16) 1.527(3) C(16)-C(17) 1.500(3) C(17)-H(17A) 0.9700 C(17)-H(17B) 0.9700

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O(1)-C(11)-C(12) 126.18(14) C(10)-C(11)-C(12) 118.57(14) C(13)-C(12)-C(11) 119.83(14) C(13)-C(12)-O(2) 117.94(14) C(11)-C(12)-O(2) 122.20(13) C(12)-C(13)-C(8) 122.36(15) C(12)-C(13)-H(13) 118.8 C(8)-C(13)-H(13) 118.8 O(1)-C(14)-C(15) 113.21(16) O(1)-C(14)-H(14A) 108.9 C(15)-C(14)-H(14A) 108.9 O(1)-C(14)-H(14B) 108.9 C(15)-C(14)-H(14B) 108.9 H(14A)-C(14)-H(14B) 107.8 F(2)-C(15)-F(1) 106.73(15) F(2)-C(15)-C(14) 109.90(16) F(1)-C(15)-C(14) 107.21(17) F(2)-C(15)-C(16) 107.11(17) F(1)-C(15)-C(16) 106.26(15) C(14)-C(15)-C(16) 118.98(14) F(3)-C(16)-F(4) 106.37(16) F(3)-C(16)-C(17) 108.01(15) F(4)-C(16)-C(17) 110.43(16) F(3)-C(16)-C(15) 108.17(15) F(4)-C(16)-C(15) 107.64(15) C(17)-C(16)-C(15) 115.80(16) O(2)-C(17)-C(16) 112.37(14) O(2)-C(17)-H(17A) 109.1 C(16)-C(17)-H(17A) 109.1 O(2)-C(17)-H(17B) 109.1 C(16)-C(17)-H(17B) 109.1 H(17A)-C(17)-H(17B) 107.9 _____________________________________________________________ Symmetry transformations used to generate equivalent atoms: #1 -x,y,-z+1/2

Table 4. Anisotropic displacement parameters (Å2x 103) for cd16512. The anisotropic displacement factor exponent takes the form: -22[ h2 a*2U11 + ... + 2 h k a* b* U12 ] ___________________________________________________________________________ ___ U11 U22 U33 U23 U13 U12 ___________________________________________________________________________ ___ F(1) 73(1) 124(1) 77(1) -54(1) 25(1) -1(1) 40

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F(2) 83(1) 150(2) 53(1) 15(1) 25(1) -41(1) F(3) 72(1) 119(1) 35(1) 8(1) -4(1) -17(1) F(4) 70(1) 51(1) 72(1) 10(1) 6(1) 6(1) O(1) 40(1) 67(1) 42(1) -11(1) 18(1) -11(1) O(2) 53(1) 37(1) 38(1) -5(1) 16(1) -1(1) C(1) 50(1) 48(1) 40(1) -3(1) 9(1) 9(1) C(2) 59(1) 66(1) 43(1) -15(1) 17(1) 2(1) C(3) 58(1) 71(1) 32(1) 1(1) 9(1) -9(1) C(4) 57(1) 56(1) 45(1) 12(1) 4(1) 8(1) C(5) 47(1) 45(1) 44(1) -1(1) 11(1) 7(1) C(6) 34(1) 40(1) 32(1) 0(1) 10(1) -1(1) C(7) 40(1) 38(1) 32(1) -1(1) 11(1) 0(1) C(8) 39(1) 38(1) 29(1) 1(1) 8(1) 1(1) C(9) 40(1) 46(1) 29(1) -7(1) 6(1) -4(1) C(10) 37(1) 48(1) 34(1) -4(1) 6(1) -10(1) C(11) 32(1) 46(1) 28(1) 2(1) 6(1) 1(1) C(12) 40(1) 34(1) 29(1) -1(1) 9(1) 1(1) C(13) 39(1) 36(1) 36(1) 0(1) 11(1) -5(1) C(14) 37(1) 72(1) 47(1) -10(1) 17(1) 2(1) C(15) 55(1) 77(1) 39(1) -10(1) 21(1) -12(1) C(16) 52(1) 60(1) 32(1) -1(1) 2(1) -4(1) C(17) 43(1) 55(1) 40(1) -12(1) 9(1) -9(1) ___________________________________________________________________________ ___ Table 5. Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å2x 10 3) for cd16512. ___________________________________________________________________________ _____ x y z U(eq) ___________________________________________________________________________ _____ H(1) 141 H(2) 576 H(3) 1335 H(4) 1697 H(5) 1302 H(9) 1526 H(10) 2290 H(13) 483 H(14A) H(14B) H(17A) H(17B)

11482 11585 8611 5607 5562 10995 10842 5231 2337 2897 299 626

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___________________________________________________________________________ _____ Table 6. Torsion angles [°] for cd16512. ________________________________________________________________ C(6)-C(1)-C(2)-C(3) -0.6(3) C(1)-C(2)-C(3)-C(4) 1.6(3) C(2)-C(3)-C(4)-C(5) -0.2(3) C(3)-C(4)-C(5)-C(6) -2.1(3) C(4)-C(5)-C(6)-C(1) 3.0(3) C(4)-C(5)-C(6)-C(7) -176.37(17) C(2)-C(1)-C(6)-C(5) -1.6(3) C(2)-C(1)-C(6)-C(7) 177.72(17) C(5)-C(6)-C(7)-C(7)#1 125.65(13) C(1)-C(6)-C(7)-C(7)#1 -53.64(18) C(5)-C(6)-C(7)-C(8) -53.3(2) C(1)-C(6)-C(7)-C(8) 127.40(17) C(7)#1-C(7)-C(8)-C(13) -50.31(17) C(6)-C(7)-C(8)-C(13)128.66(16) C(7)#1-C(7)-C(8)-C(9) 128.11(13) C(6)-C(7)-C(8)-C(9) -52.9(2) C(13)-C(8)-C(9)-C(10) 2.7(2) C(7)-C(8)-C(9)-C(10)-175.77(15) C(8)-C(9)-C(10)-C(11) -1.2(3) C(14)-O(1)-C(11)-C(10) 166.94(15) C(14)-O(1)-C(11)-C(12) -15.7(2) C(9)-C(10)-C(11)-O(1) 177.43(15) C(9)-C(10)-C(11)-C(12) -0.1(2) O(1)-C(11)-C(12)-C(13) -177.54(15) C(10)-C(11)-C(12)-C(13) -0.3(2) O(1)-C(11)-C(12)-O(2) 4.5(2) C(10)-C(11)-C(12)-O(2) -178.24(14) C(17)-O(2)-C(12)-C(13) 92.62(17) C(17)-O(2)-C(12)-C(11) -89.42(18) C(11)-C(12)-C(13)-C(8) 2.0(2) O(2)-C(12)-C(13)-C(8) -179.96(14) C(9)-C(8)-C(13)-C(12) -3.2(2) C(7)-C(8)-C(13)-C(12) 175.32(15) C(11)-O(1)-C(14)-C(15) 88.26(19) O(1)-C(14)-C(15)-F(2) 75.0(2) O(1)-C(14)-C(15)-F(1) -169.35(14) O(1)-C(14)-C(15)-C(16) -48.9(2) F(2)-C(15)-C(16)-F(3) 58.7(2) F(1)-C(15)-C(16)-F(3) -55.1(2) C(14)-C(15)-C(16)-F(3) -176.04(18) 42

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F(2)-C(15)-C(16)-F(4) -55.88(18) F(1)-C(15)-C(16)-F(4) -169.68(14) C(14)-C(15)-C(16)-F(4) 69.4(2) F(2)-C(15)-C(16)-C(17) -179.98(15) F(1)-C(15)-C(16)-C(17) 66.23(19) C(14)-C(15)-C(16)-C(17) -54.7(2) C(12)-O(2)-C(17)-C(16) 70.69(19) F(3)-C(16)-C(17)-O(2) 162.05(15) F(4)-C(16)-C(17)-O(2) -82.01(18) C(15)-C(16)-C(17)-O(2) 40.6(2) ________________________________________________________________ Symmetry transformations used to generate equivalent atoms: #1 -x,y,-z+1/2

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2,3,4,5-tetrahydrobenzo[b][1,4]dioxocane unit were synthesized. 2, The analysis of the photoluminescence emission under application of mechanical grinding and thermal treatment show AIE and MFC properties.

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“micro-aggregates”