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Download Hi-Res ImageDownload to MS-PowerPointCite This:Inorg. Chem. 2016, 55, 3, 1154-1164
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Homogeneous Photocatalytic Water Oxidation with a Dinuclear CoIII–Pyridylmethylamine Complex

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† Department of Chemistry, Graduate School of Pure and Applied Sciences, University of Tsukuba, 1-1-1 Tennoudai, Tsukuba, Ibaraki 305-8571, Japan
‡ Department of Chemistry, College of Science, Rikkyo University, 3-34-1 Nishi-Ikebukuro, Toshima, Tokyo 171-8501, Japan
§ Institute for Materials Chemistry and Engineering, Kyushu University, Motooka, Nishi-ku, Fukuoka 819-0395, Japan
⊥ Elements Strategy Initiative for Catalysts & Batteries, Kyoto University, Nishi-ku, Kyoto 615-8520, Japan
Faculty of Pharmaceutical Science at Kagawa Campus, Tokushima Bunri University, 1314-1 Shido, Sanuki, Kagawa 769-2193, Japan
∥ Department of Material and Life Science, Graduate School of Engineering, Osaka University, and ALCA, Japan Science and Technology Agency, Suita, Osaka 565-0871, Japan
⧫ Faculty of Science and Technology, Meijo University, ALCA and SENTAN, Japan Science and Technology Agency (JST), Tempaku, Nagoya, Aichi 468-8502, Japan
∞ Department of Chemistry and Nano Science, Ewha Womans University, Seoul 120-750, Korea
*E-mail: [email protected] (S. Fukuzumi).
*E-mail: [email protected] (T. Kojima).
Cite this: Inorg. Chem. 2016, 55, 3, 1154–1164
Publication Date (Web):January 21, 2016
https://doi.org/10.1021/acs.inorgchem.5b02336
Copyright © 2016 American Chemical Society
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Abstract

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A bis-hydroxo-bridged dinuclear CoIII-pyridylmethylamine complex (1) was synthesized and the crystal structure was determined by X-ray crystallography. Complex 1 acts as a homogeneous catalyst for visible-light-driven water oxidation by persulfate (S2O82–) as an oxidant with [RuII(bpy)3]2+ (bpy = 2,2′-bipyridine) as a photosensitizer affording a high quantum yield (44%) with a large turnover number (TON = 742) for O2 formation without forming catalytically active Co-oxide (CoOx) nanoparticles. In the water-oxidation process, complex 1 undergoes proton-coupled electron-transfer (PCET) oxidation as a rate-determining step to form a putative dinuclear bis-μ-oxyl CoIII complex (2), which has been suggested by DFT calculations. Catalytic water oxidation by 1 using [RuIII(bpy)3]3+ as an oxidant in a H216O and H218O mixture was examined to reveal an intramolecular O–O bond formation in the two-electron-oxidized bis-μ-oxyl intermediate, prior to the O2 evolution.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.5b02336.

  • Summary of absorption maxima, FTICR CSI-MS spectrum, ORTEP drawings of complex 1, O2 evolution profiles, 1H NMR spectra, DLS results, cyclic voltammograms, gas chromatograms, time profiles of the absorbance changes of [RuIII(bpy)3]3+ at 460 nm, ESI-TOF-MS spectrum, SEM images of ITO electrodes, and DFT-optimized structures (PDF)

  • Cartesian coordinates of the DFT-optimized structure of complex 2 and the μ:η2,η2-peroxo complex (Tables S3–S5) (PDF)

  • Crystallographic data for complex 1 (CIF)

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