Structural Study on Highly Oxidized States of a Water Oxidation Complex [RuIII(bpy)2(H2O)]2(μ-O) 4+ by Ruthenium K-Edge X-ray Absorption Fine Structure Spectroscopy

Kaoru Okamoto, Jun Miyawaki, Kensuke Nagai, Daiju Matsumura, Akihiro Nojima, Toshihiko Yokoyama, Hiroshi Kondoh, Toshiaki Ohta

研究成果: Article査読

17 被引用数 (Scopus)

抄録

The oxidation-induced structural change of a water-oxidizing diruthenium complex, [(bpy)2(H2O)RuIII(μ-O)Ru III(OH2)(bpy)2]4+ (bpy = 2,2′-bipyridine), was investigated by means of X-ray absorption spectroscopy. Ru K-edge XANES (X-ray absorption near-edge structure) spectra from the acidic solution and solid precipitates obtained by oxidation showed that the absorption edge shifts toward higher energy with a preedge feature slightly more enhanced than those of the lower oxidation states. This indicates that the higher oxidation state has a lower symmetry due to shortening of the Ru-O bonds that originated from the water ligands. The EXAFS (extended X-ray absorption fine structure) spectra were similar to those of the lower oxidation states, whose analysis revealed the existence of short Ru-O double bonds and an almost linear Ru-O-Ru angle (169 ± 2°). Ab initio EXAFS simulations for several possible structural models suggest that the dimeric structure is maintained during the water oxidation reaction.

本文言語English
ページ(範囲)8682-8689
ページ数8
ジャーナルInorganic Chemistry
42
26
DOI
出版ステータスPublished - 2003 12 29
外部発表はい

ASJC Scopus subject areas

  • 物理化学および理論化学
  • 無機化学

フィンガープリント

「Structural Study on Highly Oxidized States of a Water Oxidation Complex [Ru<sup>III</sup>(bpy)<sub>2</sub>(H<sub>2</sub>O)]<sub>2</sub>(μ-O) <sup>4+</sup> by Ruthenium K-Edge X-ray Absorption Fine Structure Spectroscopy」の研究トピックを掘り下げます。これらがまとまってユニークなフィンガープリントを構成します。

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