120th General Meeting of the KCS

Type Poster Presentation
Area Inorganic Chemistry
Room No. Exhibition Hall 2+3
Time 10월 19일 (목요일) 11:00~12:30
Code INOR.P-37
Subject Solar-Driven Water Oxidation by p-Benzoquinone Derivatives with Non-Heme Ion Complexes
Authors Young Hyun Hong, Yong-Min Lee1, Wonwoo Nam2,*, Shunichi Fukuzumi3,*
Department of Chemistry and Nano Science, Ewha Womans University, Korea
1Research Institute for Basic Sciences, Ewha Womans University, Korea
2Department of Chemistry, Ewha Womans University, Korea
3Graduate School of Science and Engineering, Meijo University, Japan
Abstract In photosystem II (PSII), solar-driven water oxidation occurs using plastoquinone (PQ) as an oxidant to produce dioxygen (O2) and plastoquinol (PQH2). An early claim to achieve solar-driven water oxidation by p-benzoquinone with a di-μ-oxo bridged manganese complex to evolve dioxygen was later withdrawn (Science 1974, 184, 375 & Science 1974, 185, 376). Since then, neither the stoichiometry nor the intermediate of photodriven water oxidation by quinones has been well established. We report herein photodriven water oxidation by p-benzoquinone derivatives such as 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) with a non-heme iron(II) complex ([(N4Py)FeII]2+: N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine) in acetonitrile (MeCN) containing H2O (0.50 M). Photoirradiation of an MeCN solution of DDQ (0.50 mM) and [(N4Py)FeII]2+ (0.20 mM) and H2O (0.50 M) with a Xenon lamp resulted in O2 evolution (0.25 mM) in 3 h. The formation of DDQH2 was confirmed by the absorption and 1H NMR spectra. The mechanism of photocatalytic oxidation of H2O by DDQ with [(N4Py)FeII]2+ will be discussed including the role of the oxidized [(N4Py)FeIV(O)]2+.
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