Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: 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:
ORCiD logo [1]; ORCiD logo [1];  [2]; ORCiD logo [2];  [2];  [3]
+ Show Author Affiliations
  1. Brookhaven National Lab. (BNL), Upton, NY (United States)
  2. Czech Academy of Sciences, Prague (Czech Republic)
  3. 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.
Copy to clipboard
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
Copy to clipboard
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.
Copy to clipboard
@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}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acs.jpcb.9b08151
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 2 works
Citation information provided by
Web of Science

Figures / Tables:

Figure 1 Figure 1: Optimized structures (b3lyp/6-31g(d)) of 1. The neutral (left) is a nearly dodecahedryl closo-carborane having a C-C bond length of 1.62 Å. In the radical anion the C-C bond length expands to 2.39 Å and further in the dianion to 2.55 Å to become a nido structure (right).
All figures and tables (24 total)
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

On the Theory of Electron‐Transfer Reactions. VI. Unified Treatment for Homogeneous and Electrode Reactions
journal, July 1965

  • Marcus, R. A.
  • The Journal of Chemical Physics, Vol. 43, Issue 2
  • DOI: 10.1063/1.1696792

On the Theory of Oxidation‐Reduction Reactions Involving Electron Transfer. I
journal, May 1956

  • Marcus, R. A.
  • The Journal of Chemical Physics, Vol. 24, Issue 5
  • DOI: 10.1063/1.1742723

Reorganization Energy of the Initial Electron-Transfer Step in Photosynthetic Bacterial Reaction Centers
journal, January 1998

A photoelectron spectroscopic and computational study of the o -dicarbadodecaborane parent anion
journal, June 2016

  • Bowen, Kit
  • The Journal of Chemical Physics, Vol. 144, Issue 22
  • DOI: 10.1063/1.4953773

Electron-Transfer Reactions with Significant Changes in Structure. Unsymmetrical Crowded Ethylenes
journal, December 2006

  • Macías-Ruvalcaba, Norma A.; Evans, Dennis H.
  • The Journal of Physical Chemistry B, Vol. 110, Issue 48
  • DOI: 10.1021/jp065634s

Kinetics of Multielectron Transfers and Redox-Induced Structural Changes in N -Aryl-Expanded Pyridiniums: Establishing Their Unusual, Versatile Electrophoric Activity
journal, August 2015

  • Lachmanová, Štěpánka; Dupeyre, Grégory; Tarábek, Ján
  • Journal of the American Chemical Society, Vol. 137, Issue 35
  • DOI: 10.1021/jacs.5b05545

Indirect Determination of Self-Exchange Electron Transfer Rate Constants
journal, August 1998

  • Nelsen, Stephen F.; Ismagilov, Rustem F.; Gentile, Kevin E.
  • Journal of the American Chemical Society, Vol. 120, Issue 32
  • DOI: 10.1021/ja9810890

Self-exchange reactions of cobalt complexes and implications concerning redox reactivity of vitamin B12
journal, January 1972

  • Rillema, D. Paul; Endicott, John F.; Kane-Maguire, Noel A. P.
  • Journal of the Chemical Society, Chemical Communications, Issue 9
  • DOI: 10.1039/c39720000495

Comparison of proton- and electron-transfer equilibriums and rates for tetraalkylhydrazines
journal, December 1981

  • Nelsen, Stephen F.; Kinlen, Patrick J.; Evans, Dennis H.
  • Journal of the American Chemical Society, Vol. 103, Issue 24
  • DOI: 10.1021/ja00414a002

Mechanism of Cobalt Self-Exchange Electron Transfer
journal, September 2013

  • Ullman, Andrew M.; Nocera, Daniel G.
  • Journal of the American Chemical Society, Vol. 135, Issue 40
  • DOI: 10.1021/ja404469y

The LEAF picosecond pulse radiolysis facility at Brookhaven National Laboratory
journal, November 2004

  • Wishart, James F.; Cook, Andrew R.; Miller, John R.
  • Review of Scientific Instruments, Vol. 75, Issue 11
  • DOI: 10.1063/1.1807004

Evidence for a two-step electron-transfer process in the electrode reactions of tetraisopropylhydrazine, tetracyclohexylhydrazine and their radical cation salts
journal, May 2000

  • Hee Hong, Sun; Evans, Dennis H.; Nelsen, Stephen F.
  • Journal of Electroanalytical Chemistry, Vol. 486, Issue 1
  • DOI: 10.1016/S0022-0728(00)00137-6

The transfer of electrons in the carborane series
journal, October 1970

  • Zakharkin, L. I.; Kalinin, V. N.
  • Bulletin of the Academy of Sciences of the USSR Division of Chemical Science, Vol. 19, Issue 10
  • DOI: 10.1007/BF00861511

1,2-Dehydro-o-carborane
journal, May 1990

  • Gingrich, Henry L.; Ghosh, Tirthankar; Huang, Qiurong
  • Journal of the American Chemical Society, Vol. 112, Issue 10
  • DOI: 10.1021/ja00166a080

New methods for the accurate determination of extinction and diffusion coefficients of aromatic and heteroaromatic radical anions in N,N-dimethylformamide
journal, August 1998

  • Pedersen, Steen U.; Bo Christensen, Torben; Thomasen, Tove
  • Journal of Electroanalytical Chemistry, Vol. 454, Issue 1-2
  • DOI: 10.1016/S0022-0728(98)00195-8

On the theory of electron transfer reactions. The naphthalene−·/TCNQ system
journal, November 1977

Effect of free energy on rates of electron transfer between molecules
journal, September 1984

  • Miller, John R.; Beitz, James V.; Huddleston, R. Kurt
  • Journal of the American Chemical Society, Vol. 106, Issue 18
  • DOI: 10.1021/ja00330a004

Theory of highly exothermic electron transfer reactions
journal, March 1982

  • Marcus, R. A.; Siders, Paul
  • The Journal of Physical Chemistry, Vol. 86, Issue 5
  • DOI: 10.1021/j100394a009

Theoretical Treatment of the Kinetics of Diffusion-Limited Reactions
journal, July 1957

Estimation of inner shell Marcus terms for amino nitrogen compounds by molecular orbital calculations
journal, February 1987

  • Nelsen, Stephen F.; Blackstock, Silas C.; Kim, Yaesil
  • Journal of the American Chemical Society, Vol. 109, Issue 3
  • DOI: 10.1021/ja00237a007

p -Carborane Conjugation in Radical Anions of Cage–Cage and Cage–Phenyl Compounds
journal, January 2018

  • Cook, Andrew R.; Valášek, Michal; Funston, Alison M.
  • The Journal of Physical Chemistry A, Vol. 122, Issue 3
  • DOI: 10.1021/acs.jpca.7b10885

Wasserstoffüberspannung und Struktur der Doppelschicht
journal, January 1933

    Sort by:
    [ × clear filter / sort ]

    Figures / Tables found in this record:

    Figure 1 (p. 5)figure
    Chart 1 (p. 6)figure
    Figure 2 (p. 8)figure
    Figure 3 (p. 11)figure
    Figure 4 (p. 13)figure
    Figure 5 (p. 15)figure
    Figure 6 (p. 15)figure
    Figure 7 (p. 16)figure
    Figure 8 (p. 17)figure
    Figure 9 (p. 18)figure
    Table 1 (p. 20)table
    Figure 10 (p. 26)figure
    Figure S1 (p. 34)figure
    Figure S2 (p. 36)figure
    Figure S3 (p. 37)figure
    Figure S4 (p. 38)figure
    Figure S5 (p. 39)figure
    Figure S6 (p. 39)figure
    Figure S7 (p. 40)figure
    Table S1 (p. 41)table
    Figure S8 (p. 42)figure
    Figure S9 (p. 42)figure
    Figure S10 (p. 43)figure
    Figure S11 (p. 44)figure
      [ × clear filter / sort ]
      Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.

      Similar Records in DOE PAGES and OSTI.GOV collections: