Consecutive Ligand‐Based Electron Transfer in New Molecular Copper‐Based Water Oxidation Catalysts
| Autor: | Gil-Sepulcre, Marcos, Garrido-Barros, Pablo, Oldengott, Jan, Funes-Ardoiz, Ignacio, Bofill, Roger, Sala, Xavier, Benet-Buchholz, Jordi, Llobet, Antoni, 0000-0002-2839-8108, 0000-0002-1489-3386, 0000-0002-5843-9660, 0000-0002-6176-5272 |
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| Rok vydání: | 2021 |
| Předmět: |
Reaction mechanisms
First-row transition metal complexes Context (language use) water splitting Redox Redox non-innocent ligand Catalysis first-row transition metal complexes Electron transfer Bipyridine chemistry.chemical_compound Transition metal water oxidation catalysis redox non-innocent ligand Water splitting Research Articles Water Oxidation Catalysis | Hot Paper Water oxidation catalysis Chemistry Ligand General Medicine General Chemistry Combinatorial chemistry reaction mechanisms Research Article |
| Zdroj: | Angewandte Chemie (International Ed. in English) RIUR. Repositorio Institucional de la Universidad de La Rioja instname |
| ISSN: | 1521-3773 1433-7851 |
| Popis: | 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. 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. |
| Databáze: | OpenAIRE |
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