Photoisomerization and proton-coupled electron transfer (PCET) promoted water oxidation by mononuclear cyclometalated ruthenium catalysts |
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Authors: | Padhi Sumanta Kumar Fukuda Ryoichi Ehara Masahiro Tanaka Koji |
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Institution: | Department of Life and Coordination-Complex Molecular Science, Institute for Molecular Science, 5-1, Higashiyama, Myodaiji, Okazaki, Aichi 444-8787, Japan. |
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Abstract: | Photoisomeric transformations in ruthenium polypyridyl complexes have been rarely reported. Herein we report the geometrical transformation of cyclometalated trans-Ru(tpy)(PAD)(OH(2))](+) (1](+)) to the cis-Ru(tpy)(PAD)(OH(2))](+) (1a](+)) (tpy = 2,2';6',2"-terpyridine, PAD = 2-(pyrid-2'-yl)acridine) isomer upon irradiation of visible light (λ ≥420 nm). Due to a proton-induced tautomeric equilibrium between the Ru-C bond and Ru═C coordination, the π* energy levels of PADH are lower than those of tpy by 12.61 and 12.24 kcal mol(-1), respectively, in 1](+) and 1a](+). Isomers 1](+) and 1a](+) both act as catalytic oxygen-evolving complexes (OECs) chemically as well as electrochemically. |
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