Effect of position of polyether attachment on the electron self-exchange activation barrier energies of redox polyether hybrid molten salts

V. Enders Dickinson, Hitoshi Masui, Mary Elizabeth Williams, Royce W. Murray

Research output: Contribution to journalArticle

34 Citations (Scopus)

Abstract

We have synthesized highly viscous, room temperature molten salts by associating [M(bpy)3]2+ cations (M = Ru or Co, bpy = 4,4′-bipyridine) with polyether-tailed 2-sulfobenzoate anions. Microelectrode voltammetry in the undiluted melts yields, on the basis of the coupling of electron hopping with physical diffusion, electron self exchange rate constants for the CoII/I and RuIII/II couples. Activation studies show that homogeneous electron transfers in the melts have large activation barriers (34-39 kJ/mol) that are similar to those of melts in which the polyether chains are covalently attached to the [M(bpy)3]2+ cations via 4,4′-bipyridine ester linkages (26-29 kJ/mol) and the counterion is perchlorate. The similarity of the activation barriers indicates that the large activation barriers do not result from a peculiar inner-sphere reorganizational barrier term caused by covalent linkage of the "solvent" (the polyether chains) to the bipyridine ligands. Also reported are physical diffusion constants, ionic conductivities, and viscosities. The number of ethylene oxide segments in the polyether tails seems to be an important determinant of physical diffusion rates and viscosity.

Original languageEnglish (US)
Pages (from-to)11028-11035
Number of pages8
JournalJournal of Physical Chemistry B
Volume103
Issue number50
StatePublished - Dec 16 1999

Fingerprint

Polyethers
molten salts
Energy barriers
attachment
Molten materials
Ion exchange
Salts
Chemical activation
activation
Electrons
linkages
Cations
electrons
Positive ions
Viscosity
viscosity
cations
Ethylene Oxide
electron diffusion
energy

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry

Cite this

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abstract = "We have synthesized highly viscous, room temperature molten salts by associating [M(bpy)3]2+ cations (M = Ru or Co, bpy = 4,4′-bipyridine) with polyether-tailed 2-sulfobenzoate anions. Microelectrode voltammetry in the undiluted melts yields, on the basis of the coupling of electron hopping with physical diffusion, electron self exchange rate constants for the CoII/I and RuIII/II couples. Activation studies show that homogeneous electron transfers in the melts have large activation barriers (34-39 kJ/mol) that are similar to those of melts in which the polyether chains are covalently attached to the [M(bpy)3]2+ cations via 4,4′-bipyridine ester linkages (26-29 kJ/mol) and the counterion is perchlorate. The similarity of the activation barriers indicates that the large activation barriers do not result from a peculiar inner-sphere reorganizational barrier term caused by covalent linkage of the {"}solvent{"} (the polyether chains) to the bipyridine ligands. Also reported are physical diffusion constants, ionic conductivities, and viscosities. The number of ethylene oxide segments in the polyether tails seems to be an important determinant of physical diffusion rates and viscosity.",
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Effect of position of polyether attachment on the electron self-exchange activation barrier energies of redox polyether hybrid molten salts. / Enders Dickinson, V.; Masui, Hitoshi; Williams, Mary Elizabeth; Murray, Royce W.

In: Journal of Physical Chemistry B, Vol. 103, No. 50, 16.12.1999, p. 11028-11035.

Research output: Contribution to journalArticle

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N2 - We have synthesized highly viscous, room temperature molten salts by associating [M(bpy)3]2+ cations (M = Ru or Co, bpy = 4,4′-bipyridine) with polyether-tailed 2-sulfobenzoate anions. Microelectrode voltammetry in the undiluted melts yields, on the basis of the coupling of electron hopping with physical diffusion, electron self exchange rate constants for the CoII/I and RuIII/II couples. Activation studies show that homogeneous electron transfers in the melts have large activation barriers (34-39 kJ/mol) that are similar to those of melts in which the polyether chains are covalently attached to the [M(bpy)3]2+ cations via 4,4′-bipyridine ester linkages (26-29 kJ/mol) and the counterion is perchlorate. The similarity of the activation barriers indicates that the large activation barriers do not result from a peculiar inner-sphere reorganizational barrier term caused by covalent linkage of the "solvent" (the polyether chains) to the bipyridine ligands. Also reported are physical diffusion constants, ionic conductivities, and viscosities. The number of ethylene oxide segments in the polyether tails seems to be an important determinant of physical diffusion rates and viscosity.

AB - We have synthesized highly viscous, room temperature molten salts by associating [M(bpy)3]2+ cations (M = Ru or Co, bpy = 4,4′-bipyridine) with polyether-tailed 2-sulfobenzoate anions. Microelectrode voltammetry in the undiluted melts yields, on the basis of the coupling of electron hopping with physical diffusion, electron self exchange rate constants for the CoII/I and RuIII/II couples. Activation studies show that homogeneous electron transfers in the melts have large activation barriers (34-39 kJ/mol) that are similar to those of melts in which the polyether chains are covalently attached to the [M(bpy)3]2+ cations via 4,4′-bipyridine ester linkages (26-29 kJ/mol) and the counterion is perchlorate. The similarity of the activation barriers indicates that the large activation barriers do not result from a peculiar inner-sphere reorganizational barrier term caused by covalent linkage of the "solvent" (the polyether chains) to the bipyridine ligands. Also reported are physical diffusion constants, ionic conductivities, and viscosities. The number of ethylene oxide segments in the polyether tails seems to be an important determinant of physical diffusion rates and viscosity.

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