Mechanistic Insight into the Electronic Influences Imposed by Substituent Variation in Polyazine‐Bridged Ruthenium(II)/Rhodium(III) Supramolecules | Zendy

White Travis A. | Zendy; Mallalieu Hannah E. | Zendy; Wang Jing | Zendy; Brewer Karen J. | Zendy

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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.

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