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Title: Electrical conductivity in two mixed-valence liquids

Abstract

In this work, two different room-temperature liquid systems were investigated, both of which conduct a DC electrical current without decomposition or net chemical transformation. DC electrical conductivity is possible in both cases because of the presence of two different oxidation states of a redox-active species. One system is a 1:1 molar mixture of n-butylferrocene (BuFc) and its cation bis(trifluoromethane)sulfonimide salt, [BuFc+][NTf2-], while the other is a 1:1 molar mixture of TEMPO and its cation bis(trifluoromethane)sulfonimide salt, [TEMPO+][NTf2-]. The TEMPO–[TEMPO+][NTf2-] system is notable in that it is an electrically conducting liquid in which the conductivity originates from an organic molecule in two different oxidation states, with no metals present. Single-crystal X-ray diffraction of [TEMPO+][NTf2-] revealed a complex structure with structurally different cation–anion interactions for cis- and trans [NTf2-] conformers. The electron transfer self-exchange rate constant for BuFc/BuFc+ in CD3CN was determined by 1H NMR spectroscopy to be 5.4 × 106 M-1 s-1. The rate constant allowed calculation of an estimated electrical conductivity of 7.6 × 10-5 Ω-1 cm-1 for BuFc–[BuFc+][NTf2-], twice the measured value of 3.8 × 10-5 Ω-1 cm-1. Similarly, a previously reported self-exchange rate constant for TEMPO/TEMPO+ in CH3CN led to an estimated conductivity of 1.3 × 10-4 Ω-1more » cm-1 for TEMPO–[TEMPO+][NTf2-], a factor of about 3 higher than the measured value of 4.3 × 10-5 Ω-1 cm-1.« less

Authors:
 [1];  [1];  [1];  [1]
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  1. Univ. of Alabama, Tuscaloosa, AL (United States)
Publication Date:
Research Org.:
Univ. of Alabama, Tuscaloosa, AL (United States)
Sponsoring Org.:
USDOE Office of Nuclear Energy (NE)
OSTI Identifier:
1592722
Grant/Contract Number:  
NE0000366
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP
Additional Journal Information:
Journal Volume: 17; Journal Issue: 21; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Yao, Wenzhi, Kelley, Steven P., Rogers, Robin D., and Vaid, Thomas P. Electrical conductivity in two mixed-valence liquids. United States: N. p., 2015. Web. doi:10.1039/C5CP01172H.
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Yao, Wenzhi, Kelley, Steven P., Rogers, Robin D., & Vaid, Thomas P. Electrical conductivity in two mixed-valence liquids. United States. https://doi.org/10.1039/C5CP01172H
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Yao, Wenzhi, Kelley, Steven P., Rogers, Robin D., and Vaid, Thomas P. Tue . "Electrical conductivity in two mixed-valence liquids". United States. https://doi.org/10.1039/C5CP01172H. https://www.osti.gov/servlets/purl/1592722.
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@article{osti_1592722,
title = {Electrical conductivity in two mixed-valence liquids},
author = {Yao, Wenzhi and Kelley, Steven P. and Rogers, Robin D. and Vaid, Thomas P.},
abstractNote = {In this work, two different room-temperature liquid systems were investigated, both of which conduct a DC electrical current without decomposition or net chemical transformation. DC electrical conductivity is possible in both cases because of the presence of two different oxidation states of a redox-active species. One system is a 1:1 molar mixture of n-butylferrocene (BuFc) and its cation bis(trifluoromethane)sulfonimide salt, [BuFc+][NTf2-], while the other is a 1:1 molar mixture of TEMPO and its cation bis(trifluoromethane)sulfonimide salt, [TEMPO+][NTf2-]. The TEMPO–[TEMPO+][NTf2-] system is notable in that it is an electrically conducting liquid in which the conductivity originates from an organic molecule in two different oxidation states, with no metals present. Single-crystal X-ray diffraction of [TEMPO+][NTf2-] revealed a complex structure with structurally different cation–anion interactions for cis- and trans [NTf2-] conformers. The electron transfer self-exchange rate constant for BuFc/BuFc+ in CD3CN was determined by 1H NMR spectroscopy to be 5.4 × 106 M-1 s-1. The rate constant allowed calculation of an estimated electrical conductivity of 7.6 × 10-5 Ω-1 cm-1 for BuFc–[BuFc+][NTf2-], twice the measured value of 3.8 × 10-5 Ω-1 cm-1. Similarly, a previously reported self-exchange rate constant for TEMPO/TEMPO+ in CH3CN led to an estimated conductivity of 1.3 × 10-4 Ω-1 cm-1 for TEMPO–[TEMPO+][NTf2-], a factor of about 3 higher than the measured value of 4.3 × 10-5 Ω-1 cm-1.},
doi = {10.1039/C5CP01172H},
journal = {Physical Chemistry Chemical Physics. PCCP},
number = 21,
volume = 17,
place = {United States},
year = {Tue May 05 00:00:00 EDT 2015},
month = {Tue May 05 00:00:00 EDT 2015}
}
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https://doi.org/10.1039/C5CP01172H
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