Inorganic Chemistry, Vol.51, No.7, 4343-4351, 2012
Biscyclometalated Ruthenium Complexes Bridged by 3,3',5,5'-Tetrakis(N-methylbenzimidazol-2-yl)biphenyl: Synthesis and Spectroscopic and Electronic Coupling Studies
A series of biscyclometalated ruthenium complexes bridged by the title ligand were prepared by either an oxidative dimerization of corresponding monometallic complexes or treatment of the bridging ligand with Ru(L)Cl-3 (L = capping ligand). The electronic properties of these complexes were examined by electrochemical and spectroscopic analysis and DFT/TDDFT calculations. The degree of metal-metal electronic coupling of these complexes was estimated on the basis of intervalence charge-transfer transition analysis of corresponding mixed-valent complexes. These studies indicated that the electronic coupling was strongly dependent on the electronic nature of the terminal ligands. A hole-transfer superexchange mechanism was used to understand the underlying electron-transfer processes.