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

Naoyuki Imai, Tomohdco Hamaguchi, Tadashi Yamaguchi, Tasuku Ito

Research output: Contribution to journalArticle

Abstract

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.

Original languageEnglish
Pages (from-to)207-214
Number of pages8
JournalMaterials Science- Poland
Volume21
Issue number2
Publication statusPublished - 2003
Externally publishedYes

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Ruthenium
Pyridine
ruthenium
electron transfer
valence
pyridines
Electrons
Azabicyclo Compounds
octanes
Spectroelectrochemistry
Pyrazines
Dimers
pyrazines
Rate constants
Thermodynamic stability
Ligands
dimers
thermodynamics
ligands
pyridine

ASJC Scopus subject areas

  • Materials Science(all)
  • Condensed Matter Physics
  • Mechanical Engineering
  • Mechanics of Materials

Cite this

Intramolecular electron transfer on the vibrational timescale in mixed valence ruthenium clusters. / Imai, Naoyuki; Hamaguchi, Tomohdco; Yamaguchi, Tadashi; Ito, Tasuku.

In: Materials Science- Poland, Vol. 21, No. 2, 2003, p. 207-214.

Research output: Contribution to journalArticle

Imai, Naoyuki ; Hamaguchi, Tomohdco ; Yamaguchi, Tadashi ; Ito, Tasuku. / Intramolecular electron transfer on the vibrational timescale in mixed valence ruthenium clusters. In: Materials Science- Poland. 2003 ; Vol. 21, No. 2. pp. 207-214.
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abstract = "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.",
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N2 - 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.

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