TY - JOUR
T1 - Consecutive Ligand-Based Electron Transfer in New Molecular Copper-Based Water Oxidation Catalysts
AU - Gil-Sepulcre, Marcos
AU - Garrido-Barros, Pablo
AU - Oldengott, Jan
AU - Funes-Ardoiz, Ignacio
AU - Bofill, Roger
AU - Sala, Xavier
AU - Benet-Buchholz, Jordi
AU - Llobet, Antoni
N1 - Funding Information:
The authors gratefully acknowledge the support from Ministerio de Ciencia, Innovación y Universidades and FEDER (PID2019‐111617RB‐I00 and PID2019‐104171RB‐I00), AGAUR 2017‐SGR‐1631, Ministerio de Ciencia e Inovación for a Severo Ochoa Excellence Accreditation grant 2020–2023 (CEX2019‐000925‐S, MIC/AEI), DFG research fellowship (OL‐562) and EU‐funded LICROX FET project (Grant agreement 951843). P.G.‐B. acknowledges the “La Caixa” Foundation for the Ph.D. grant.
Funding Information:
The authors gratefully acknowledge the support from Ministerio de Ciencia, Innovaci?n y Universidades and FEDER (PID2019-111617RB-I00 and PID2019-104171RB-I00), AGAUR 2017-SGR-1631, Ministerio de Ciencia e Inovaci?n for a Severo Ochoa Excellence Accreditation grant 2020?2023 (CEX2019-000925-S, MIC/AEI), DFG research fellowship (OL-562) and EU-funded LICROX FET project (Grant agreement 951843). P.G.-B. acknowledges the ?La Caixa? Foundation for the Ph.D. grant.
Publisher Copyright:
© 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH
PY - 2021/8/16
Y1 - 2021/8/16
N2 - 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 H2LNn− (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.
AB - 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 H2LNn− (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.
KW - first-row transition metal complexes
KW - reaction mechanisms
KW - redox non-innocent ligand
KW - water oxidation catalysis
KW - water splitting
UR - http://www.scopus.com/inward/record.url?scp=85110071168&partnerID=8YFLogxK
U2 - 10.1002/anie.202104020
DO - 10.1002/anie.202104020
M3 - Article
C2 - 34015172
AN - SCOPUS:85110071168
SN - 1433-7851
VL - 60
SP - 18639
EP - 18644
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 34
ER -