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

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Abstract

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.

Original languageEnglish
Pages (from-to)8682-8689
Number of pages8
JournalInorganic Chemistry
Volume42
Issue number26
DOIs
Publication statusPublished - 2003 Dec 29
Externally publishedYes

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X ray absorption fine structure spectroscopy
Ruthenium
ruthenium
fine structure
Oxidation
oxidation
Water
X ray absorption
water
spectroscopy
x rays
X ray absorption spectroscopy
Precipitates
precipitates
absorption spectroscopy
Ligands
ligands
shift
symmetry

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

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

In: Inorganic Chemistry, Vol. 42, No. 26, 29.12.2003, p. 8682-8689.

Research output: Contribution to journalArticle

Okamoto, Kaoru ; Miyawaki, Jun ; Nagai, Kensuke ; Matsumura, Daiju ; Nojima, Akihiro ; Yokoyama, Toshihiko ; Kondoh, Hiroshi ; Ohta, Toshiaki. / 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. In: Inorganic Chemistry. 2003 ; Vol. 42, No. 26. pp. 8682-8689.
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