The Impact of Huge Structural Changes on Electron Transfer and Measurement of Redox Potentials: Reduction of ortho-12-Carborane
Abstract
A massive structural change accompanies electron capture by the 1,2-dicarba-closo-dodecaborane cage molecule (1). Bimolecular electron transfer (ET) by pulse radiolysis found a reduction potential of E0 = –1.92 V vs Fc+/0 for 1 and rate constants that slowed greatly for ET to or from 1 when the redox partner had a potential near this E0. Moreover, two electrochemical techniques could detect no current at potentials near E0, finding instead peaks or polarographic waves near –3.1 V, which is 1.2 V more negative than E0. Voltammetry could determine rate constants, but only near –3.1 V. DigiSim simulations can describe the irreversible voltammograms but require electrochemical rate constants near 1 × 10–10 cm/s at E0, a factor of 10–10 relative to molecules undergoing facile ET. This factor of 10–10 compared to ~10–5 for bimolecular ET introduces a puzzle. This puzzle can be understood as a manifestation of one of the “Frumkin Effects” in which only part of the applied voltage is available to drive ET at the electrode.
- Authors:
-
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Czech Academy of Sciences, Prague (Czech Republic)
- Univ. of Colorado, Boulder, CO (United States); Czech Academy of Sciences, Prague (Czech Republic)
- Publication Date:
- Research Org.:
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1572367
- Report Number(s):
- BNL-212237-2019-JAAM
Journal ID: ISSN 1520-6106; TRN: US2001322
- Grant/Contract Number:
- SC0012704
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
- Additional Journal Information:
- Journal Volume: 123; Journal Issue: 45; Journal ID: ISSN 1520-6106
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 14 SOLAR ENERGY; Homogeneous vs heterogeneous electron transfer; reorganization energy; cyclic voltammetry; pulse radiolysis; overpotential; Frumkin Effect; free energy relation; carborane
Citation Formats
Miller, John R., Cook, Andrew R., Šimková, Ludmila, Pospíšil, Lubomír, Ludvík, Jiří, and Michl, Josef. The Impact of Huge Structural Changes on Electron Transfer and Measurement of Redox Potentials: Reduction of ortho-12-Carborane. United States: N. p., 2019.
Web. doi:10.1021/acs.jpcb.9b08151.
Miller, John R., Cook, Andrew R., Šimková, Ludmila, Pospíšil, Lubomír, Ludvík, Jiří, & Michl, Josef. The Impact of Huge Structural Changes on Electron Transfer and Measurement of Redox Potentials: Reduction of ortho-12-Carborane. United States. https://doi.org/10.1021/acs.jpcb.9b08151
Miller, John R., Cook, Andrew R., Šimková, Ludmila, Pospíšil, Lubomír, Ludvík, Jiří, and Michl, Josef. Fri .
"The Impact of Huge Structural Changes on Electron Transfer and Measurement of Redox Potentials: Reduction of ortho-12-Carborane". United States. https://doi.org/10.1021/acs.jpcb.9b08151. https://www.osti.gov/servlets/purl/1572367.
@article{osti_1572367,
title = {The Impact of Huge Structural Changes on Electron Transfer and Measurement of Redox Potentials: Reduction of ortho-12-Carborane},
author = {Miller, John R. and Cook, Andrew R. and Šimková, Ludmila and Pospíšil, Lubomír and Ludvík, Jiří and Michl, Josef},
abstractNote = {A massive structural change accompanies electron capture by the 1,2-dicarba-closo-dodecaborane cage molecule (1). Bimolecular electron transfer (ET) by pulse radiolysis found a reduction potential of E0 = –1.92 V vs Fc+/0 for 1 and rate constants that slowed greatly for ET to or from 1 when the redox partner had a potential near this E0. Moreover, two electrochemical techniques could detect no current at potentials near E0, finding instead peaks or polarographic waves near –3.1 V, which is 1.2 V more negative than E0. Voltammetry could determine rate constants, but only near –3.1 V. DigiSim simulations can describe the irreversible voltammograms but require electrochemical rate constants near 1 × 10–10 cm/s at E0, a factor of 10–10 relative to molecules undergoing facile ET. This factor of 10–10 compared to ~10–5 for bimolecular ET introduces a puzzle. This puzzle can be understood as a manifestation of one of the “Frumkin Effects” in which only part of the applied voltage is available to drive ET at the electrode.},
doi = {10.1021/acs.jpcb.9b08151},
journal = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},
number = 45,
volume = 123,
place = {United States},
year = {2019},
month = {10}
}
Web of Science
Figures / Tables:

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