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Combined Effects of Hemicolligation and Ion Pairing on Reduction Potentials of Biphenyl Radical Cations

Journal Article · · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
 [1];  [1];  [1]
  1. Brookhaven National Laboratory (BNL), Upton, NY (United States)
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Here, formal reduction potentials of highly oxidizing and short-lived radical cations of substituted biphenyls generated by pulse radiolysis in 1,2-dichloroethane (DCE) were measured using a redox equilibrium ladder method. The effect of halide ion–radical interactions on reduction potentials of biphenyls was examined by utilizing the ability of DCE to release Cl– in the vicinity of the radical cation. The Hammett correlation of measured potentials across a range of over 700 mV shows saturation at high Hammett sigma values. This effect has been explained by both ion-pairing and hemicolligation interactions between biphenyl radical cations and Cl– and appears to modulate reduction potentials by as much as 400 mV. This finding offers a convenient way to manipulate the energetics of electron transfer involving organic redox species.

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)
Grant/Contract Number:
SC0012704
OSTI ID:
2203264
Report Number(s):
BNL--224911-2023-JAAM
Journal Information:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 38 Vol. 127; ISSN 1089-5639
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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Figures / Tables (62)

Scheme 1(p. 6)figure Scheme 1
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Related Subjects

14 SOLAR ENERGY
aromatic compounds
biphenyl radical cation
cations
hemicolligation
hydrocarbons
ion pairing
ions
pulse radiolysis
redox reactions