prelims, contents pages

Polyhedron 86, 28 January 2015

Contents lists available at ScienceDirect

Polyhedron journal homepage: www.elsevier.com/locate/poly

Contents

Jean-François Halet and Jean-René Hamon Polyhedron 86 (2015) 1 Foreword to the special issue of Polyhedron dedicated to Professor Claude Lapinte

Ulrike Pfaff, Alexander Hildebrandt, Marcus Korb and Heinrich Lang Polyhedron 86 (2015) 2 The influence of an ethynyl spacer on the electronic properties in 2,5-ferrocenyl-substituted heterocycles

Siu-Tung Lam, Nianyong Zhu, Vonika Ka-Man Au and Vivian Wing-Wah Yam Polyhedron 86 (2015) 10 Synthesis, characterization, electrochemistry and photophysical studies of rhenium(I) tricarbonyl diimine complexes with carboxaldehyde alkynyl ligands

Elsevier Ltd.

A series of 2,5-(FcCBC)2-cC4H2E (E = NPh, S, O) was prepared using the Sonogashira C,C cross-coupling protocol. The results of electro- and spectroelectrochemical measurements in comparison to 2,5-Fc2-cC4H2E are discussed. The occurrence of IVCT absorptions in the UV–Vis/NIR spectra shows that the 2,5-diethynylferrocenyl heterocycles are class II systems according to Robin and Day.

A class of rhenium(I) tricarbonyl diimine complexes of carboxaldehyde alkynyl was synthesized and characterized, and the X-ray crystal structure of one of the complexes was determined. The redox properties were studied by electrochemistry. The complexes were found to emit at 630–672 nm in solution, assignable to a 3 MLCT origin.

Polyhedron 86 (2015) 17 Synthesis, photophysical and electrochemical study of diisocyano-bridged homodinuclear rhenium(I) diimine complexes

A new series of luminescent diisocyanidebridged homodinuclear Re(I) complexes and their mononuclear analogues have been synthesized. The X-ray crystal structures of two of the dinuclear complexes were determined. The photophysical and electrochemical properties of these complexes have been investigated.

Normalized Emission Intensity

Chi-Chiu Ko, Apple Wai-Yi Cheung and Shek-Man Yiu

Contents

Normalized Emission Intensity

vi

500

550

600

650

700

750

800

450

Wavelength / nm

Didier Astruc, Yanlan Wang, Amalia Rapakousiou, Abdou Diallo, Rodrigue Djeda, Jaime Ruiz and Catia Ornelas

500

550

600

650

700

Wavelength / nm

The construction, redox properties and applications of organoiron dendrimers are discussed in this micro-review.

Polyhedron 86 (2015) 24 Organoiron-mediated synthesis and redox activity of organoiron-containing dendrimers

Kevin B. Vincent, Matthias Parthey, Dmitry S. Yufit, Martin Kaupp and Paul J. Low Polyhedron 86 (2015) 31 Synthesis and redox properties of mono-, diand tri-metallic platinum-ethynyl complexes based on the transPt(C6H4N{C6H4OCH3-4}2)(CBCR)(PPh3)2 motif

Michael I. Bruce, Marcus L. Cole, Benjamin G. Ellis, Maryka Gaudio, Brian K. Nicholson, Christian R. Parker, Brian W. Skelton and Allan H. White Polyhedron 86 (2015) 43 The series of carbon-chain complexes {Ru(dppe)Cp*}2{l-(CBC)x} (x = 4–8, 11): Synthesis, structures, properties and some reactions

The compounds trans-Pt(CBCAr)(C6H4NAr2) (PPh3)2 (4a), trans-Pt(CBCC6H4NAr2)(C6H4 NAr2)(PPh3)2 (4b), {trans-Pt(C6H4NAr2) (PPh3)2}2(l-CBC-1,4-C6H4CBC) (5) and N{C6H4CBCPt(C6H4NAr2)(PPh3)2}3 (6) have been studied using a combination of electrochemical, spectroelectrochemical and quantum chemical analyses, which reveal weak electronic coupling between the amine moieties in the formally organic mixed-valence complexes formed on one-electron oxidation.

Pd(0)/Cu(I)-catalysed reactions between iodo- or diiodo-alkynes and (phosphine)gold-substituted alkynyl-ruthenium complexes have given {Ru(dppe)Cp*}2 {l-(CBC)x} (x = 4–8, 11). Their redox properties have been measured, and seven X-ray structures are described.

{Ln M}

I

{Ln M}

(C

C)y

(C

(C

R

C)(x+y)

C)x

Au(PPh3 )

I

Pd(0) / Cu(I)

R

{Ln M}

(C

(C

C)y

C)(2x+y)

I

{ML n}

Contents

Polyhedron 86 (2015) 57 A rhodium(I) dicarbonyl complex with a redoxactive ferrocenyl phosphine-NHC ligand: Enhanced reactivity of the metal centre through ferrocene oxidation

Areej Merhi, Guillaume Grelaud, Nicolas Ripoche, Adam Barlow, Marie P. Cifuentes, Mark G. Humphrey, Frédéric Paul and Christine O. Paul-Roth Polyhedron 86 (2015) 64 A zinc(II) tetraphenylporphyrin peripherally functionalized with redox-active ‘‘trans[(g5-C5H5)Fe(g5-C5H4)CBC](j2-dppe)2Ru(CBC)-’’ substituents: Linear electrochromism and thirdorder nonlinear optics

Anita Grupp, Jan Fiedler and Wolfgang Kaim Polyhedron 86 (2015) 71 UV–Vis-NIR spectroelectrochemical study of tetrathiorhenate-bridged diruthenium complexes

The behaviour of a new dicarbonyl rhodium(I) complex bearing an electroactive ferrocenyl phosphine-NHC ligand towards oxidation has been studied, proving that the electron density at the rhodium centre could be tuned by oxidation of the ferrocenyl group. This difference has been highlighted by infra-red spectroscopic measurements.

The synthesis and characterization of a new Zn(II) tetraphenylporphyrin derivative (4) featuring eight redox-active centers at the periphery (four trans-Ru(j2-dppe)2 fragments and four ferrocenyl endgroups) is reported, and its linear spectroelectrochemistry and third-order nonlinear optical properties at 560 nm and 630 nm are discussed.

The suitability of a tetrathiometallate bridge for allowing electrochemical and electronic communication between two redox-active transition metal centers has been studied for the system [(acac)2Ru (l-S)2Re(l-S)2Ru(acac)2]n, n = 0. A typical inter-valence charge transfer absorption was observed by spectroelectrochemisttry in the near infrared.

20 15 ε / 103M-1cm-1

Nathalie Debono, Jean-Claude Daran, Rinaldo Poli and Agnès Labande

vii

n = (-) → (0)

10 5 0 500

Jie-Wen Ying, Zhi Cao, Charles Campana, You Song, Jing-Lin Zuo, Sarah F. Tyler and Tong Ren Polyhedron 86 (2015) 76 Linear trimers of diruthenium linked by polyyndiyl or phenylenediethynyl bridges: A family of unique electronic wires

Successful modulation of electronic coupling within [Ru2]–linker–[Ru2]–linker– [Ru2] systems with linkers as butadiyn-diyl, hexadiyn-diyl and phenylenediethynyl.

1000 1500 λ [nm]

2000

viii

Néstor Novoa, Frédéric Justaud, Paul Hamon, Thierry Roisnel, Olivier Cador, Boris Le Guennic, Carolina Manzur, David Carrillo and Jean-René Hamon Polyhedron 86 (2015) 81 Doubly phenoxide-bridged binuclear copper(II) complexes with ono tridentate schiff base ligand: Synthesis, structural, magnetic and theoretical studies

Kathryn A.E. Roberts, Neil J. Brown, Hannah N. Roberts, Joseph J.W. McDouall, Paul J. Low and Mark W. Whiteley Polyhedron 86 (2015) 89 Electronic structure and spectroscopy of the cycloheptatrienyl molybdenum halide complexes [MoBrL2(g-C7H7)]n+ (L2 = 2CO, n = 0; L2 = 2,2¢-bipyridyl, n = 0 or 1)

Karima Deramchi, Boubekeur Maouche, Samia Kahlal and Jean-Yves Saillard Polyhedron 86 (2015) 98 A DFT investigation of some (formally) redox isomerization reactions of bis(pentalenyl)iron and bis(azulenyl)iron

Contents

Reactions of tridentate ONO-donor Schiff base ligand H2L, derived from the condensation of 1-anisyl-1,3-butanedione and 2aminophenol, with Cu(NO3)2Æ3H2O afford two doubly phenoxo bridged di-copper(II) complexes: [Cu2L2] and [(py-tBu)2Cu2L2] depending on the nitrogenous base used. [Cu2L2] shows a strong antiferromagnetic coupling (J = )397 cm)1).

Electronic structure calculations (DFT, B3LYP/Def2-SVP) on the half-sandwich cycloheptatrienyl molybdenum complexes [MoBrL2(g-C7H7)] (L2 = 2 CO or 2,2¢-bipyridyl) reveal that in each case the HOMO features significant metal dz2 character but the composition of the LUMO is L2 dependent. TD-DFT methods have been employed to analyse the experimental UV–Vis electronic absorption spectra of these complexes.

The intramolecular interconversion of the Fe(C8H6)2 and Fe(C10H8)2 isomers are symmetry-dependent and related to the nodal properties of the LUMO and HOMO of their C2v intermediate, respectively.

HOMO

LUM LU UMO O

C2

C’2

C2v

Yuya Tanaka, Takuya Ishisaka, Takashi Koike and Munetaka Akita Polyhedron 86 (2015) 105 Synthesis and properties of diiron complexes with heteroaromatic linkers: An approach for modulation of organometallic molecular wire

Molecular wires with two redox active organometallic Cp*(dppe)Fe(•CBC• units bridged with various heteroaromatic linkers have been synthesized. Heteroatoms in the molecular wires play important roles in controlling electron transfer between metal termini.

Ph Fe Ph P P Ph Ph

X=

Cs

Fe Ph P Ph Ph P Ph

X e

S

O

N

Contents

Yuta Hasegawa, Haruki Nakamura, Yohei Hattori, Ken Hoshiko, Tetsuro Kusamoto, Masaki Murata, Shoko Kume and Hiroshi Nishihara Polyhedron 86 (2015) 111 Geometric and electrochemical properties of complexes consisting of two aminonaphthoquinone-bound Schiff-base ligands and MnII, FeII, NiII, CuII, or ZnII

Braulio Aranda, Pedro Aguirre, Sergio A. Moya, Mickaële Bonneau, J.A. Gareth Williams, Loic Toupet, Muriel Escadeillas, Hubert Le Bozec and Véronique Guerchais Polyhedron 86 (2015) 120 Luminescent bis-cyclometallated iridium(III) complexes containing phosphine-based ligands: Influence of the P^N bridge

G. Joel Meyer, Gabriel B. Hall, Elliott R. Smith, Takahiro Sakamoto, Dennis L. Lichtenberger and Richard S. Glass Polyhedron 86 (2015) 125 Through space interaction between ferrocenes mediated by a thioether

Keith Man-Chung Wong, Chunyan Wang, Ho-Chuen Lam and Nianyong Zhu Polyhedron 86 (2015) 133 Bichromophoric rhodamine-rhenium(I) and iridium(III) sensory system: Synthesis, characterizations, photophysical and selective metal ions binding studies

ix

Novel metal complexes with aminonaphthoquinone-bound Schiff-base ligands were prepared. The isostructural complexes formed NNN-type octahedral coordination geometry in crystals. Structural and electrochemical studies revealed that the central metal ion played important roles in both the molecular and the electronic structures of the complexes, controlling their electron-responsive properties (redox functionalities).

Three cationic bis-cyclometallated iridium complexes with 4-methyl-2-phenylpyridine (ppyMe) as the C^N-cyclometallated ligands and the P^N-ligands, 8-(diphenylphosphino)quinoline (Ph2Pqn, L1), 2-(diphenylphosphinoamino)pyridine (Ph2PNHpy, L2) and 2-(diphenylphosphinoamino)pyrimidine (Ph2 PNHpym, L3), were prepared, and their X-ray crystallography, and photoluminescence were investigated. The complexes 2–3 featuring the P–NH–N ligands emit in the blue region, whereas the P–CAr–N-incorporating complex 1 displays orange photoluminescence.

Geometrically constrained 2,6-diferrocenylphenylthioethers were synthesized and characterized. Through space interaction between the ferrocene moieties mediated by sulfur were evaluated by electrochemistry, photoelectron spectroscopy and UV– Vis–NIR spectroscopy of the mixed valence species. Enhanced interaction mediated by sulfur was ascribed to electrostatic interaction enhanced by the polarizability of sulfur.

A new class of rhenium(I) tricarbonyl diimine complexes tethered with rhodamine derivative, have been synthesized, and their photophysical and selective ionbinding properties investigated, with the comparison of the cyclometalated iridium(III) system.

Me

N C

+

Ir

Ph2 P XH N

C N

Me

Ph2P PF6

N L1

HN Ph2P

N L2

N HN N Ph2P L3

x

Contents

Ashley R. Head, Sharon K. Renshaw, Andrew B. Uplinger, Jeffrey R. Lomprey, John P. Selegue and Dennis L. Lichtenberger Polyhedron 86 (2015) 141 Experimental measure of metal–alkynyl electronic structure interactions by photoelectron spectroscopy: (g5-C5H5)Ru(CO)2CBCMe and [(g5-C5H5)Ru(CO)2]2(l-CBC)

Jean-Pierre Launay Polyhedron 86 (2015) 151 An orbital approach of electron transfer in multisite systems. Implications for carbon-rich spacers

UV photoelectron spectroscopy was used to probe the electronic structure of the alkynyl ligand of (g5-C5H5)Ru(CO)2CBCMe and [(g5-C5H5)Ru(CO)2]2(l-CBC). The filled/filled interaction between the ligand p and metal d orbitals, the backbonding capacity of the alkynyl ligand, and the electronic communication between the metal centers is quantified from the ionization energies.

Isolobal analogy between organometallic and organic sites; link with solid-state concepts. Electronic interaction through overlap of ‘‘magnetic-like’’ orbitals: decay of the HOMO of fragments with distance, case of even and odd bridges, and aromatic linkers. Electron–phonon interaction (Holstein and Peierls types). A three-state model for M–L–M systems.

D

1

2

D

3

D

D

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