Solvent dynamical control of ultrafast ground state electron transfer: Implications for class II-III mixed valency

Benjamin James Lear, Starla D. Glover, J. Catherine Salsman, Casey H. Londergan, Clifford P. Kubiak

Research output: Contribution to journalArticle

47 Citations (Scopus)

Abstract

We relate the solvent and temperature dependence of the rates of intramolecular electron transfer (ET) of mixed valence complexes of the type {[Ru3O(OAc)6(CO)(L)]2-BL}-1, where L = pyridyl ligand and BL = pyrazine. Complexes were reduced chemically or electrochemically to obtain the mixed valence anions in seven solvents: acetonitrile, methylene chloride, dimethylformamide, tetrahydrofuran, dimethylsulfoxide, chloroform, and hexamethylphosphoramide. Rate constants for intramolecular ET were estimated by simulating the observed degree of ν(CO) IR band shape coalescence in the mixed valence state. Correlations between rate constants for ET and solvent properties including static dielectric constant, optical dielectric constant, the quantity 1/εop - 1/εS, microscopic solvent polarity, viscosity, cardinal rotational moments of inertia, and solvent relaxation times were examined. In the temperature study, the complexes displayed a sharp increase in the k et as the freezing points of the solvents methylene chloride and acetonitrile were approached. The solvent phase transition causes a localized-to-delocalized transition in the mixed valence ions and an acceleration in the rate of ET. This is explained in terms of decoupling the slower solvent motions involved in the frequency factor νN which increases the value of νN. The observed solvent and temperature dependence of the ket for these complexes is used in order to formulate a new definition for Robin-Day class II-III mixed valence compounds. Specifically, it is proposed that class II-III compounds are those for which thermodynamic properties of the solvent exert no control over ket, but the dynamic properties of the solvent still influence ket.

Original languageEnglish (US)
Pages (from-to)12772-12779
Number of pages8
JournalJournal of the American Chemical Society
Volume129
Issue number42
DOIs
StatePublished - Oct 24 2007

Fingerprint

Ground state
Electrons
Methylene Chloride
Dichloromethane
Carbon Monoxide
Acetonitrile
Temperature
Rate constants
Permittivity
Hempa
Pyrazines
Dimethylformamide
Songbirds
Phase Transition
Chloroform
Chlorine compounds
Dimethyl Sulfoxide
Coalescence
Thermodynamics
Viscosity

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Lear, Benjamin James ; Glover, Starla D. ; Salsman, J. Catherine ; Londergan, Casey H. ; Kubiak, Clifford P. / Solvent dynamical control of ultrafast ground state electron transfer : Implications for class II-III mixed valency. In: Journal of the American Chemical Society. 2007 ; Vol. 129, No. 42. pp. 12772-12779.
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Solvent dynamical control of ultrafast ground state electron transfer : Implications for class II-III mixed valency. / Lear, Benjamin James; Glover, Starla D.; Salsman, J. Catherine; Londergan, Casey H.; Kubiak, Clifford P.

In: Journal of the American Chemical Society, Vol. 129, No. 42, 24.10.2007, p. 12772-12779.

Research output: Contribution to journalArticle

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T1 - Solvent dynamical control of ultrafast ground state electron transfer

T2 - Implications for class II-III mixed valency

AU - Lear, Benjamin James

AU - Glover, Starla D.

AU - Salsman, J. Catherine

AU - Londergan, Casey H.

AU - Kubiak, Clifford P.

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N2 - We relate the solvent and temperature dependence of the rates of intramolecular electron transfer (ET) of mixed valence complexes of the type {[Ru3O(OAc)6(CO)(L)]2-BL}-1, where L = pyridyl ligand and BL = pyrazine. Complexes were reduced chemically or electrochemically to obtain the mixed valence anions in seven solvents: acetonitrile, methylene chloride, dimethylformamide, tetrahydrofuran, dimethylsulfoxide, chloroform, and hexamethylphosphoramide. Rate constants for intramolecular ET were estimated by simulating the observed degree of ν(CO) IR band shape coalescence in the mixed valence state. Correlations between rate constants for ET and solvent properties including static dielectric constant, optical dielectric constant, the quantity 1/εop - 1/εS, microscopic solvent polarity, viscosity, cardinal rotational moments of inertia, and solvent relaxation times were examined. In the temperature study, the complexes displayed a sharp increase in the k et as the freezing points of the solvents methylene chloride and acetonitrile were approached. The solvent phase transition causes a localized-to-delocalized transition in the mixed valence ions and an acceleration in the rate of ET. This is explained in terms of decoupling the slower solvent motions involved in the frequency factor νN which increases the value of νN. The observed solvent and temperature dependence of the ket for these complexes is used in order to formulate a new definition for Robin-Day class II-III mixed valence compounds. Specifically, it is proposed that class II-III compounds are those for which thermodynamic properties of the solvent exert no control over ket, but the dynamic properties of the solvent still influence ket.

AB - We relate the solvent and temperature dependence of the rates of intramolecular electron transfer (ET) of mixed valence complexes of the type {[Ru3O(OAc)6(CO)(L)]2-BL}-1, where L = pyridyl ligand and BL = pyrazine. Complexes were reduced chemically or electrochemically to obtain the mixed valence anions in seven solvents: acetonitrile, methylene chloride, dimethylformamide, tetrahydrofuran, dimethylsulfoxide, chloroform, and hexamethylphosphoramide. Rate constants for intramolecular ET were estimated by simulating the observed degree of ν(CO) IR band shape coalescence in the mixed valence state. Correlations between rate constants for ET and solvent properties including static dielectric constant, optical dielectric constant, the quantity 1/εop - 1/εS, microscopic solvent polarity, viscosity, cardinal rotational moments of inertia, and solvent relaxation times were examined. In the temperature study, the complexes displayed a sharp increase in the k et as the freezing points of the solvents methylene chloride and acetonitrile were approached. The solvent phase transition causes a localized-to-delocalized transition in the mixed valence ions and an acceleration in the rate of ET. This is explained in terms of decoupling the slower solvent motions involved in the frequency factor νN which increases the value of νN. The observed solvent and temperature dependence of the ket for these complexes is used in order to formulate a new definition for Robin-Day class II-III mixed valence compounds. Specifically, it is proposed that class II-III compounds are those for which thermodynamic properties of the solvent exert no control over ket, but the dynamic properties of the solvent still influence ket.

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