Redox Polyetber Hybrid Copper Bipyridine Complex Molten Salts

Franzpeter Emmenegger, Mary Elizabeth Williams, Royce W. Murray

Research output: Contribution to journalArticle

13 Citations (Scopus)

Abstract

The covalent attachment of poly(ethylene oxide) chains to metal bipyridine complexes produces viscous molecular melts with sufficient ionic conductivity to permit microelectrode voltammetry. This paper describes the use of this chemistry to prepare a new copper complex with "tailed" bipyridine ligands, [Cu(bpy(CO2MePEG-350)2)2]-(ClO 4)2, where MePEG-350 is methyl poly(ethylene glycol) with molecular weight 350 g mol-1. The coupling of physical diffusion with electron hopping during voltammetry allows measurement of the electron self-exchange rate constant, kEX, for the Cu(II/I) couple. Activation studies indicate the reaction to be nearly adiabatic, with an activation barrier larger than expected for purely inner-sphere rearrangements. This study also examines the depression of both electron transport and ionic conductivity caused by the addition of 1.4 M LiClO4) to the undiluted room-temperature melt.

Original languageEnglish (US)
Pages (from-to)3146-3151
Number of pages6
JournalInorganic chemistry
Volume36
Issue number14
StatePublished - Dec 1 1997

Fingerprint

molten salts
Ionic conductivity
Voltammetry
Molten materials
Copper
Salts
Chemical activation
copper
ion currents
Electrons
Microelectrodes
Metal complexes
Polyethylene oxides
activation
Polyethylene glycols
Rate constants
electrons
Molecular weight
ethylene oxide
Ligands

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Emmenegger, Franzpeter ; Williams, Mary Elizabeth ; Murray, Royce W. / Redox Polyetber Hybrid Copper Bipyridine Complex Molten Salts. In: Inorganic chemistry. 1997 ; Vol. 36, No. 14. pp. 3146-3151.
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Emmenegger, F, Williams, ME & Murray, RW 1997, 'Redox Polyetber Hybrid Copper Bipyridine Complex Molten Salts', Inorganic chemistry, vol. 36, no. 14, pp. 3146-3151.

Redox Polyetber Hybrid Copper Bipyridine Complex Molten Salts. / Emmenegger, Franzpeter; Williams, Mary Elizabeth; Murray, Royce W.

In: Inorganic chemistry, Vol. 36, No. 14, 01.12.1997, p. 3146-3151.

Research output: Contribution to journalArticle

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AU - Emmenegger, Franzpeter

AU - Williams, Mary Elizabeth

AU - Murray, Royce W.

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N2 - The covalent attachment of poly(ethylene oxide) chains to metal bipyridine complexes produces viscous molecular melts with sufficient ionic conductivity to permit microelectrode voltammetry. This paper describes the use of this chemistry to prepare a new copper complex with "tailed" bipyridine ligands, [Cu(bpy(CO2MePEG-350)2)2]-(ClO 4)2, where MePEG-350 is methyl poly(ethylene glycol) with molecular weight 350 g mol-1. The coupling of physical diffusion with electron hopping during voltammetry allows measurement of the electron self-exchange rate constant, kEX, for the Cu(II/I) couple. Activation studies indicate the reaction to be nearly adiabatic, with an activation barrier larger than expected for purely inner-sphere rearrangements. This study also examines the depression of both electron transport and ionic conductivity caused by the addition of 1.4 M LiClO4) to the undiluted room-temperature melt.

AB - The covalent attachment of poly(ethylene oxide) chains to metal bipyridine complexes produces viscous molecular melts with sufficient ionic conductivity to permit microelectrode voltammetry. This paper describes the use of this chemistry to prepare a new copper complex with "tailed" bipyridine ligands, [Cu(bpy(CO2MePEG-350)2)2]-(ClO 4)2, where MePEG-350 is methyl poly(ethylene glycol) with molecular weight 350 g mol-1. The coupling of physical diffusion with electron hopping during voltammetry allows measurement of the electron self-exchange rate constant, kEX, for the Cu(II/I) couple. Activation studies indicate the reaction to be nearly adiabatic, with an activation barrier larger than expected for purely inner-sphere rearrangements. This study also examines the depression of both electron transport and ionic conductivity caused by the addition of 1.4 M LiClO4) to the undiluted room-temperature melt.

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