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Title: The Impact of Huge Structural Changes on Electron Transfer and Measurement of Redox Potentials: Reduction of ortho-12-Carborane

Journal Article · · Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
ORCiD logo [1]; ORCiD logo [1];  [2]; ORCiD logo [2];  [2];  [3]
  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)
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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.

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0012704
OSTI ID:
1572367
Report Number(s):
BNL-212237-2019-JAAM; TRN: US2001322
Journal Information:
Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry, Vol. 123, Issue 45; ISSN 1520-6106
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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Figures / Tables (24)

Figure 1(p. 5)figure Figure 1
Chart 1(p. 6)figure Chart 1
Figure 2(p. 8)figure Figure 2
Figure 3(p. 11)figure Figure 3
Figure 4(p. 13)figure Figure 4
Figure 5(p. 15)figure Figure 5
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Figure 9(p. 18)figure Figure 9
Table 1(p. 20)table Table 1
Figure 10(p. 26)figure Figure 10
Figure S1(p. 34)figure Figure S1
Figure S2(p. 36)figure Figure S2
Figure S3(p. 37)figure Figure S3
Figure S4(p. 38)figure Figure S4
Figure S5(p. 39)figure Figure S5
Figure S6(p. 39)figure Figure S6
Figure S7(p. 40)figure Figure S7
Table S1(p. 41)table Table S1
Figure S8(p. 42)figure Figure S8
Figure S9(p. 42)figure Figure S9
Figure S10(p. 43)figure Figure S10
Figure S11(p. 44)figure Figure S11

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Related Subjects

14 SOLAR ENERGY
Homogeneous vs heterogeneous electron transfer
reorganization energy
cyclic voltammetry
pulse radiolysis
overpotential
Frumkin Effect
free energy relation
carborane