title: Dinuclear Ruthenium Complex Based on a π-Extended Bridging Ligand with Redox-Active Tetrathiafulvalene and 1,10-Phenanthroline Units.
abstract: The synthesis of a π-extended bridging ligand with both redox-active tetrathiafulvalene (TTF) and 1,10-phenanthroline (phen) units, namely, bis(1,10-phenanthro[5,6-b])tetrathiafulvalene (BPTTF), was realized via a self-coupling reaction. Using this ligand and Ru(tbbpy)2Cl2 (tbbpy = 4,4'-di-tert-butyl-2,2'-bipyridine), the dinuclear ruthenium(II) compound [{Ru(tbbpy)2}2(BPTTF)](PF6)4 (1) has been obtained by microwave-assisted synthesis. Structural characterization of 1 revealed a crossed arrangement of the TTF moieties on adjacent dimers within the crystal structure. The optical and redox properties of 1 were investigated using electrochemical, spectroelectrochemical, electron paramagnetic resonance (EPR), and absorption spectroscopic studies combined with theoretical calculations. One exhibits a rich electrochemical behavior owing to the multiple redox-active centers. Interestingly, both the ligand BPTTF and the ruthenium compound 1 are EPR-active in the solid state owing to intramolecular charge-transfer processes. The results demonstrate that the TTF-annulated bis(phen) ligand is a promising bridging ligand to construct oligomeric or polymeric metal complexes with multiple redox-active centers.
authors.affiliation: State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Collaborative Innovation Center of Advanced Microstructures, Nanjing University , Nanjing 210093, P. R. China.
authors.forename: Bin
authors.initials: B
authors.lastname: Chen
authors.affiliation: State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Collaborative Innovation Center of Advanced Microstructures, Nanjing University , Nanjing 210093, P. R. China.
authors.forename: Zhong-Peng
authors.initials: ZP
authors.lastname: Lv
authors.affiliation: School of Chemistry, The University of Sydney , New South Wales 2006, Australia.
authors.forename: Carol
authors.initials: C
authors.lastname: Hua
authors.affiliation: School of Chemistry, The University of Sydney , New South Wales 2006, Australia.
authors.forename: Chanel F
authors.initials: CF
authors.lastname: Leong
authors.affiliation: School of Chemistry and Photon Science Institute, The University of Manchester , Manchester M13 9PL, United Kingdom.
authors.forename: Floriana
authors.initials: F
authors.lastname: Tuna
authors.affiliation: School of Chemistry, The University of Sydney , New South Wales 2006, Australia.
authors.forename: Deanna M
authors.initials: DM
authors.lastname: D'Alessandro
authors.affiliation: School of Chemistry and Photon Science Institute, The University of Manchester , Manchester M13 9PL, United Kingdom.
authors.forename: David
authors.initials: D
authors.lastname: Collison
authors.affiliation: State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Collaborative Innovation Center of Advanced Microstructures, Nanjing University , Nanjing 210093, P. R. China.
authors.forename: Jing-Lin
authors.initials: JL
authors.lastname: Zuo