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Solvent Control of Ligand–Metal Electron Transfer in Mononuclear Copper Complexes with Redox‐Active Bisguanidine Ligands
Author(s) -
Schrempp David F.,
Kaifer Elisabeth,
Himmel HansJörg
Publication year - 2018
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201800525
Subject(s) - chemistry , non innocent ligand , redox , ligand (biochemistry) , intramolecular force , electron transfer , copper , combinatorial chemistry , metal , photochemistry , inorganic chemistry , stereochemistry , organic chemistry , biochemistry , receptor
Intramolecular electron transfer (IET) processes between the metal and a redox‐active ligand in a transition‐metal complex are currently intensively studied, as they represent key steps of some redox‐catalytic reactions in synthetic chemistry and of some enzymatic redox reactions in biological systems. Using a combination of experimental results and quantum chemical calculations, we herein examine in detail the role of the solvent polarity and seemingly small modifications at the redox‐active ligand on IET processes in mononuclear copper complexes with redox‐active bisguanidine ligands. A direct and simple correlation between the coordination mode and the electronic structure in these complexes is established, assisting in the fine‐tuning of the ligand properties for optimal promotion of IET.