Solid-state voltammetry in a polyether-tailed Co tris(bipyridine) molten salt: Ion pairing effects

Mary Elizabeth Williams; Hitoshi Masui; Royce W. Murray

doi:10.1021/jp001545i

Solid-state voltammetry in a polyether-tailed Co tris(bipyridine) molten salt: Ion pairing effects

Mary Elizabeth Williams, Hitoshi Masui, Royce W. Murray

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Abstract

This paper describes experiments exploring the role of the redox-inactive counterion in hybrid redox polyether molten salts. Because these materials are undiluted, they intrinsically contain "solvent-separated ion pairs", where the "solvent" is the polyether tail attached to the redox moiety. Measurements on molten salts with polyether-derivatized Co(II) tris(bipyridine) cations show that stronger forms of ionic association can occur between the complex and its counterion, leading in the case of triflate counterion to additional voltammetric waves. The rate of conversion between differently associated Co(II) complexes in the molten salt is sluggish. Ion-association equilibria exist between Co(II) and Fe(II) tris(bipyridine) cations and their perchlorate or triflate counterions even in dilute dimethoxyethane solutions, as shown by solubility and microelectrode voltammetry.

Original language	English (US)
Pages (from-to)	10699-10706
Number of pages	8
Journal	Journal of Physical Chemistry B
Volume	104
Issue number	45
DOIs	https://doi.org/10.1021/jp001545i
State	Published - Nov 16 2000

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Surfaces, Coatings and Films
Materials Chemistry

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title = "Solid-state voltammetry in a polyether-tailed Co tris(bipyridine) molten salt: Ion pairing effects",

abstract = "This paper describes experiments exploring the role of the redox-inactive counterion in hybrid redox polyether molten salts. Because these materials are undiluted, they intrinsically contain {"}solvent-separated ion pairs{"}, where the {"}solvent{"} is the polyether tail attached to the redox moiety. Measurements on molten salts with polyether-derivatized Co(II) tris(bipyridine) cations show that stronger forms of ionic association can occur between the complex and its counterion, leading in the case of triflate counterion to additional voltammetric waves. The rate of conversion between differently associated Co(II) complexes in the molten salt is sluggish. Ion-association equilibria exist between Co(II) and Fe(II) tris(bipyridine) cations and their perchlorate or triflate counterions even in dilute dimethoxyethane solutions, as shown by solubility and microelectrode voltammetry.",

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T1 - Solid-state voltammetry in a polyether-tailed Co tris(bipyridine) molten salt

T2 - Ion pairing effects

AU - Williams, Mary Elizabeth

AU - Masui, Hitoshi

AU - Murray, Royce W.

PY - 2000/11/16

Y1 - 2000/11/16

N2 - This paper describes experiments exploring the role of the redox-inactive counterion in hybrid redox polyether molten salts. Because these materials are undiluted, they intrinsically contain "solvent-separated ion pairs", where the "solvent" is the polyether tail attached to the redox moiety. Measurements on molten salts with polyether-derivatized Co(II) tris(bipyridine) cations show that stronger forms of ionic association can occur between the complex and its counterion, leading in the case of triflate counterion to additional voltammetric waves. The rate of conversion between differently associated Co(II) complexes in the molten salt is sluggish. Ion-association equilibria exist between Co(II) and Fe(II) tris(bipyridine) cations and their perchlorate or triflate counterions even in dilute dimethoxyethane solutions, as shown by solubility and microelectrode voltammetry.

AB - This paper describes experiments exploring the role of the redox-inactive counterion in hybrid redox polyether molten salts. Because these materials are undiluted, they intrinsically contain "solvent-separated ion pairs", where the "solvent" is the polyether tail attached to the redox moiety. Measurements on molten salts with polyether-derivatized Co(II) tris(bipyridine) cations show that stronger forms of ionic association can occur between the complex and its counterion, leading in the case of triflate counterion to additional voltammetric waves. The rate of conversion between differently associated Co(II) complexes in the molten salt is sluggish. Ion-association equilibria exist between Co(II) and Fe(II) tris(bipyridine) cations and their perchlorate or triflate counterions even in dilute dimethoxyethane solutions, as shown by solubility and microelectrode voltammetry.

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Solid-state voltammetry in a polyether-tailed Co tris(bipyridine) molten salt: Ion pairing effects

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