Intramolecular electron transfer on the vibrational timescale in mixed valence ruthenium clusters

Naoyuki Imai, Tomohdco Hamaguchi, Tadashi Yamaguchi, Tasuku Ito*

*この研究の対応する著者

研究成果: Article査読

抄録

The thermodynamic stability of the mixed valence (one electron reduced) state between linked Ru3 units was studied by means of electrochemical methods for the series of the ligand-bridged triruthenium cluster dimer, [Ru3(μ-O)(n-CH3CO2) 6(CO)(L)(n-BL)Ru3(μ-O)(μ-CH3CO 2)6(CO)(L)] (BL = 1,4-pyrazine: L = 4-dimethylaminopyridine (dmap) (1a), pyridine (py) (1b), 4-cyanopyridine (cpy) (1e), 1-azabicyclo[2.2.2]octane (1d); BL = 4,4′-bipyridine: L = dmap (2a), py (2b), cpy (2c); BL = 2,7-diazapyrene: L = dmap (3a); BL = 1,4-diazabicyclo[2.2.2]octane: L = dmap (4a), py (4b), cpy (4c)). The mixed valence states undergoing rapid intramolecular electron transfers were observed by ER spectroelectrochemistry. By simulating dynamical effects on the observed v(CO) absorption bandshapes, the rate constants ke for electron transfer in the mixed valence states of la, Ib, le and Id were estimated to be 9×1011 s-1 (at room temperature (rt)), 5×1011 s-1 (at it), c.a,1×1011 s-1 (at it), and 1×1012 s-1 (at-18 °C), respectively. Possible applications of this approach to asymmetric mixed valence systems were discusssed.

本文言語English
ページ(範囲)207-214
ページ数8
ジャーナルMaterials Science- Poland
21
2
出版ステータスPublished - 2003 12月 1
外部発表はい

ASJC Scopus subject areas

  • 材料科学(全般)
  • 凝縮系物理学
  • 材料力学
  • 機械工学

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