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 language | English |
|---|---|
| Pages (from-to) | 8682-8689 |
| Number of pages | 8 |
| Journal | Inorganic Chemistry |
| Volume | 42 |
| Issue number | 26 |
| DOIs | |
| Publication status | Published - 2003 Dec 29 |
| Externally published | Yes |
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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 journal › Article
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TY - JOUR
T1 - 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
AU - Okamoto, Kaoru
AU - Miyawaki, Jun
AU - Nagai, Kensuke
AU - Matsumura, Daiju
AU - Nojima, Akihiro
AU - Yokoyama, Toshihiko
AU - Kondoh, Hiroshi
AU - Ohta, Toshiaki
PY - 2003/12/29
Y1 - 2003/12/29
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=0347594096&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=0347594096&partnerID=8YFLogxK
U2 - 10.1021/ic034373n
DO - 10.1021/ic034373n
M3 - Article
C2 - 14686845
AN - SCOPUS:0347594096
VL - 42
SP - 8682
EP - 8689
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 26
ER -