Dimerization rate of the 1-methyl-4-tert-butylpyridinyl radical and the photochemical process of the dimer cleavage. Kinetic and time-resolved ESR studies

Kimio Akiyama, Shozo Tero-Kubota, Yusaku Ikegami, Tsuneo Ikenoue

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

The 1-methyl-4-tert-butylpyridinyl radical can be in equilibrium with the 2,2 dimer which shows photolytic cleavage to generate the radical. The dimer structure was offered from the results of 1H and 13C NMR measurements. The dimerization rate (k) evaluated from the kinetic ESR measurements can be represented by log (k/M-1 s-1) = 8.55 - 2.02 (kcal/mol)/θ, where θ = 2.303RT. Time-resolved ESR experiments for the photolytic cleavage of the dimer revealed that the precursor of the radical generation was a singlet radical pair, exhibiting an A/E polarization pattern in the transient ESR spectra.

Original languageEnglish
Pages (from-to)339-342
Number of pages4
JournalJournal of physical chemistry
Volume89
Issue number2
DOIs
Publication statusPublished - 1985 Jan 1

ASJC Scopus subject areas

  • Engineering(all)
  • Physical and Theoretical Chemistry

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