Redox Polyetber Hybrid Copper Bipyridine Complex Molten Salts

Franzpeter Emmenegger; Mary Elizabeth Williams; Royce W. Murray

doi:10.1021/ic970149k

Redox Polyetber Hybrid Copper Bipyridine Complex Molten Salts

Franzpeter Emmenegger, Mary Elizabeth Williams, Royce W. Murray

Research output: Contribution to journal › Article › peer-review

13 Scopus citations

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, k_EX, 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 language	English (US)
Pages (from-to)	3146-3151
Number of pages	6
Journal	Inorganic chemistry
Volume	36
Issue number	14
DOIs	https://doi.org/10.1021/ic970149k
State	Published - 1997

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Inorganic Chemistry

Access to Document

10.1021/ic970149k

Cite this

@article{1703c1efe1c146ddad438f099a259517,

title = "Redox Polyetber Hybrid Copper Bipyridine Complex Molten Salts",

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.",

author = "Franzpeter Emmenegger and Williams, {Mary Elizabeth} and Murray, {Royce W.}",

year = "1997",

doi = "10.1021/ic970149k",

language = "English (US)",

volume = "36",

pages = "3146--3151",

journal = "Inorganic chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "14",

}

TY - JOUR

T1 - Redox Polyetber Hybrid Copper Bipyridine Complex Molten Salts

AU - Emmenegger, Franzpeter

AU - Williams, Mary Elizabeth

AU - Murray, Royce W.

PY - 1997

Y1 - 1997

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.

UR - http://www.scopus.com/inward/record.url?scp=0001461371&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0001461371&partnerID=8YFLogxK

U2 - 10.1021/ic970149k

DO - 10.1021/ic970149k

M3 - Article

AN - SCOPUS:0001461371

SN - 0020-1669

VL - 36

SP - 3146

EP - 3151

JO - Inorganic chemistry

JF - Inorganic chemistry

IS - 14

ER -

Redox Polyetber Hybrid Copper Bipyridine Complex Molten Salts

Abstract

All Science Journal Classification (ASJC) codes

Access to Document

Other files and links

Fingerprint

Cite this