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Mechanistic Insight into the Electronic Influences Imposed by Substituent Variation in Polyazine‐Bridged Ruthenium(II)/Rhodium(III) Supramolecules
Author(s) -
White Travis A.,
Mallalieu Hannah E.,
Wang Jing,
Brewer Karen J.
Publication year - 2014
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201402564
Subject(s) - bimetallic strip , rhodium , electrochemistry , ruthenium , supramolecular chemistry , cyclic voltammetry , substituent , chemistry , bridging ligand , halide , ligand (biochemistry) , atomic orbital , crystallography , stereochemistry , metal , inorganic chemistry , electrode , crystal structure , catalysis , electron , organic chemistry , physics , quantum mechanics , biochemistry , receptor
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.