Consecutive Ligand-Based Electron Transfer in New Molecular Copper-Based Water Oxidation Catalysts
Gil Sepulcre, Marcos (Barcelona Institute of Science and Technology (BIST))
Garrido Barros, Pablo (Barcelona Institute of Science and Technology (BIST))
Oldengott, Jan (Barcelona Institute of Science and Technology (BIST))
Funes-Ardoiz, Ignacio (Universitad de La Rioja)
Bofill Arasa, Roger (Universitat Autònoma de Barcelona. Departament de Química)
Sala Román, Xavier (Universitat Autònoma de Barcelona. Departament de Química)
Benet-Buchholz, Jordi (Barcelona Institute of Science and Technology (BIST))
Llobet Dalmases, Antoni (Universitat Autònoma de Barcelona. Departament de Química)

Data:	2021
Resum:	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 HLN 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. A family of Cu-based complexes bearing dianionic bpy-amidate ligands have been prepared and characterized by spectroscopic and electrochemical techniques. The new complexes are capable of performing water oxidation catalysis at overpotentials between 557-830 mV pH 11. 6. A detailed electrocatalytic study in combination with computational calculations revealed the all ligand-based nature of the electron transfer processes involved in the catalytic cycle.
Ajuts:	Agencia Estatal de Investigación PID2019-111617RB-I00 Agencia Estatal de Investigación PID2019-104171RB-I00 Agencia Estatal de Investigación CEX2019-000925-S Agència de Gestió d'Ajuts Universitaris i de Recerca 2017/SGR-1631 European Commission 951843
Drets:	Aquest document està subjecte a una llicència d'ús Creative Commons. Es permet la reproducció total o parcial, la distribució, la comunicació pública de l'obra i la creació d'obres derivades, fins i tot amb finalitats comercials, sempre i quan es reconegui l'autoria de l'obra original.
Llengua:	Anglès
Document:	Article ; recerca ; Versió publicada
Matèria:	First-row transition metal complexes ; Reaction mechanisms ; Redox non-innocent ligand ; Water oxidation catalysis ; Water splitting
Publicat a:	Angewandte Chemie (International ed. Internet), Vol. 60, Issue 34 (August 2021) , p. 18639-18644, ISSN 1521-3773

DOI: 10.1002/anie.202104020
PMID: 34015172

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