論文

査読有り 筆頭著者
2019年9月3日

Kinetics and Mechanism of Intramolecular Electron Transfer in Ru(II)–Re(I) Supramolecular CO2–Reduction Photocatalysts: Effects of Bridging Ligands

Inorganic Chemistry
  • Yasuomi Yamazaki
  • ,
  • Kei Ohkubo
  • ,
  • Daiki Saito
  • ,
  • Taiki Yatsu
  • ,
  • Yusuke Tamaki
  • ,
  • Sei’ichi Tanaka
  • ,
  • Kazuhide Koike
  • ,
  • Ken Onda
  • ,
  • Osamu Ishitani

58
17
開始ページ
11480
終了ページ
11492
記述言語
英語
掲載種別
研究論文(学術雑誌)
DOI
10.1021/acs.inorgchem.9b01256
出版者・発行元
American Chemical Society ({ACS})

The supramolecular photocatalysts in which a Ru(II) complex as a molecular redox photosensitizer unit and a Re(I) complex as a molecular catalyst unit are connected with a various alkyl or ether chain have attracted attention because they can efficiently photocatalyze CO2 reduction with high durability and high selectivity of CO formation, especially on various solid materials such as semiconductor electrodes and mesoporous organosilica. The intramolecular electron transfer from the one-electron reduced photosensitizer unit to the catalyst unit, which follows excitation of the photosensitizer unit and subsequent reductive quenching of the excited photo-sensitizer unit by a reductant, is one of the most important processes in the photocatalytic reduction of CO2. We succeeded in determining the rate constants of this intramolecular electron transfer process by using subnanosecond time-resolved IR spectroscopy. The logarithm of rate constants shows a linear relationship with the lengths of the bridging chain in the supramolecular photocatalysts with one bridging alkyl or ether chain. In conformity with the exponential decay of the wave function and the coupling element in the long-distance electron transfer, the apparent decay coefficient factor (beta) in the supramolecular photocatalysts with one bridging chain was determined to be 0.74 angstrom(-1). In the supramolecular photocatalyst with two ethylene chains connecting between the photosensitizer and catalyst units, on the other hand, the intramolecular electron transfer rate is much faster than that with only one ethylene chain. These results strongly indicate that the intramolecular electron transfer from the one-electron reduced species of the Ru photosensitizer unit to the Re catalyst unit proceeds by the through-bond mechanism.

リンク情報
DOI
https://doi.org/10.1021/acs.inorgchem.9b01256
Web of Science
https://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=JSTA_CEL&SrcApp=J_Gate_JST&DestLinkType=FullRecord&KeyUT=WOS:000484066500023&DestApp=WOS_CPL
ID情報
  • DOI : 10.1021/acs.inorgchem.9b01256
  • ISSN : 0020-1669
  • eISSN : 1520-510X
  • ORCIDのPut Code : 60600146
  • Web of Science ID : WOS:000484066500023

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