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Consecutive Ligand‐Based Electron Transfer in New Molecular Copper‐Based Water Oxidation Catalysts
Author(s) -
GilSepulcre Marcos,
GarridoBarros Pablo,
Oldengott Jan,
FunesArdoiz Ignacio,
Bofill Roger,
Sala Xavier,
BenetBuchholz Jordi,
Llobet Antoni
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202104020
Subject(s) - ligand (biochemistry) , chemistry , redox , catalysis , electrochemistry , amide , bipyridine , context (archaeology) , water splitting , electron transfer , copper , transition metal , non innocent ligand , rational design , catalytic oxidation , combinatorial chemistry , photochemistry , metal , inorganic chemistry , organic chemistry , materials science , nanotechnology , electrode , photocatalysis , crystal structure , paleontology , biochemistry , receptor , biology
Water oxidation to dioxygen is one of the key reactions that need to be mastered for the design of practical devices based on water splitting with sunlight. In this context, water oxidation catalysts based on first‐row transition metal complexes are highly desirable due to their low cost and their synthetic versatility and tunability through rational ligand design. A new family of dianionic bpy‐amidate ligands of general formula H 2 LN n − (LN is [2,2′‐bipyridine]‐6,6′‐dicarboxamide) substituted with phenyl or naphthyl redox non‐innocent moieties is described. A detailed electrochemical analysis of [(L4)Cu] 2− (L4=4,4′‐(([2,2′‐bipyridine]‐6,6′‐dicarbonyl)bis(azanediyl))dibenzenesulfonate) at pH 11.6 shows the presence of a large electrocatalytic wave for water oxidation catalysis at an η=830 mV. Combined experimental and computational evidence, support an all ligand‐based process with redox events taking place at the aryl‐amide groups and at the hydroxido ligands.