Electrochemical potential gap in radicals: Why organic radicals do not disproportionate in solution?

Oleg A. Levitskiy, Vyacheslav V. Sentyurin, Alexey V. Bogdanov, Tatiana V. Magdesieva*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

2 Citations (Scopus)

Abstract

The physical origin of the electrochemical potential gap (ΔE0 = E0Ox − E0Red) in radicals is discussed. It was shown that the EC gap in radicals is well approximated by two-electron Coulomb repulsion between the unpaired electron of the parent radical and an additional electron appeared in the SOMO after reduction. This repulsion prevents the disproportionation of radicals and makes possible their existence in solution. Assuming the density distribution of both electrons to be similar to that in the parent radical, the self-Coulomb integral of the spin density (K) provides a quantitative measure for the spin delocalization and for the estimation of a vertical electron transfer energy gap. Linear correlation between the experimentally measured electrochemical gaps and the integral K was found. Validity of the theoretical model was supported by experimental and computational data for a representative set of persistent radicals (46 examples).

Original languageEnglish
Article number142632
JournalElectrochimica Acta
Volume460
DOIs
Publication statusPublished - 20 Aug 2023
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • General Chemical Engineering
  • Electrochemistry

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