title: Efficient Light-Driven Water Oxidation Catalysis by Dinuclear Ruthenium Complexes.
abstract: Mastering the light-induced four-electron oxidation of water to molecular oxygen is a key step towards the achievement of overall water splitting to produce alternative solar fuels. In this work, we report two rugged molecular pyrazolate-based diruthenium complexes that efficiently catalyze visible-light-driven water oxidation. These complexes were fully characterized both in the solid state (by X-ray diffraction analysis) and in solution (spectroscopically and electrochemically). Benchmark performances for homogeneous oxygen production have been obtained for both catalysts in the presence of a photosensitizer and a sacrificial electron acceptor at pH 7, and a turnover frequency of up to 11.1 s(-1) and a turnover number of 5300 were obtained after three successive catalytic runs. Under the same experimental conditions with the same setup, the pyrazolate-based diruthenium complexes outperform other well-known water oxidation catalysts owing to both electrochemical and mechanistic aspects.
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans 16, 43007, Tarragona, Spain.
authors.forename: Serena
authors.initials: S
authors.lastname: Berardi
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans 16, 43007, Tarragona, Spain.
authors.forename: Laia
authors.initials: L
authors.lastname: Francàs
authors.affiliation: Institute of Inorganic Chemistry, Georg-August-University Göttingen, Tammannstraße 4, 37077, Göttingen, Germany.
authors.forename: Sven
authors.initials: S
authors.lastname: Neudeck
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans 16, 43007, Tarragona, Spain.
authors.forename: Somnath
authors.initials: S
authors.lastname: Maji
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans 16, 43007, Tarragona, Spain.
authors.forename: Jordi
authors.initials: J
authors.lastname: Benet-Buchholz
authors.affiliation: Institute of Inorganic Chemistry, Georg-August-University Göttingen, Tammannstraße 4, 37077, Göttingen, Germany. franc.meyer@chemie.uni-goettingen.de.
authors.forename: Franc
authors.initials: F
authors.lastname: Meyer
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans 16, 43007, Tarragona, Spain. allobet@iciq.cat.|Departament de Química, Universitat Autònoma de Barcelona, Cerdanyola del Vallès, 08193, Barcelona, Spain. allobet@iciq.cat.
authors.forename: Antoni
authors.initials: A
authors.lastname: Llobet
mesh_terms: D002384:Catalysis; D056831:Coordination Complexes / Q000737:chemistry*; D008027:Light; D015394:Molecular Structure; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D012428:Ruthenium / Q000737:chemistry*; D014867:Water / Q000737:chemistry*
chemical_list: D056831:Coordination Complexes; D014867:Water; D012428:Ruthenium; D010100:Oxygen
keywords: complexes; photosensitizer; redox chemistry; ruthenium; water oxidation