Enhanced photoreduction of water catalyzed by a cucurbit[8]uril-secured platinum dimer |
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Authors: | Ramin Rabbani,Sima Saeedi,Md Nazimuddin,Hé ctor Barbero,Nathalie Kyritsakas,Travis A. White,Eric Masson |
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Affiliation: | Department of Chemistry and Biochemistry, Ohio University, Athens Ohio 45701 USA.; GIR MIOMeT, IU CINQUIMA/Química Inorgánica, Facultad de Ciencias, Universidad de Valladolid, Valladolid E47011 Spain ; Molecular Tectonics Laboratory, University of Strasbourg, UMR UDS-CNRS 7140, Institut le Bel, F-67000 Strasbourg France |
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Abstract: | A cucurbit[8]uril (CB[8])-secured platinum terpyridyl chloride dimer was used as a photosensitizer and hydrogen-evolving catalyst for the photoreduction of water. Volumes of produced hydrogen were up to 25 and 6 times larger than those obtained with the corresponding free and cucurbit[7]uril-bound platinum monomer, respectively, at equal Pt concentration. The thermodynamics of the proton-coupled electron transfer from the Pt(ii)–Pt(ii) dimer to the corresponding Pt(ii)–Pt(iii)–H hydride key intermediate, as quantified by density functional theory, suggest that CB[8] secures the Pt(ii)–Pt(ii) dimer in a particularly reactive conformation that promotes hydrogen formation.The cucurbit[8]uril macrocycle can secure a platinum terpyridyl complex into a particularly reactive dimer that catalyzes the photoreduction of water. |
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