title: Mechanistic insight into the electronic influences imposed by substituent variation in polyazine-bridged ruthenium(II)/rhodium(III) supramolecules.
abstract: Unusual and unprecedented multipathway electrochemical mechanisms for a new class of supramolecular Ru/Rh bimetallic photocatalysts have been uncovered. The near isoenergetic Rh(dσ*) and bridging ligand(π*) molecular orbitals and a rate of halide loss that occurs on the cyclic voltammetry timescale provide a series of closely related complexes which display four different electrochemical mechanisms. A single complex displays two concurrent electrochemical pathways in marked contrast to all previously studied cis-[Rh(NN)(2)X(2)] motifs.
authors: Department of Chemistry, Virginia Tech, 1105 Hahn Hall South, Blacksburg, VA 24061-0212 (USA), Fax: (+1) 540-231-3255.
authors: Travis A
authors: TA
authors: White
authors: Hannah E
authors: HE
authors: Mallalieu
authors: Jing
authors: J
authors: Wang
authors: Karen J
authors: KJ
authors: Brewer
keywords: electrochemistry; polyazine; rhodium; ruthenium; supramolecular photocatalysts