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

doi:10.1021/j100248a032

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

Division of Organic- and Biomaterials Research

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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 language	English
Pages (from-to)	339-342
Number of pages	4
Journal	Journal of physical chemistry
Volume	89
Issue number	2
DOIs	https://doi.org/10.1021/j100248a032
Publication status	Published - 1985 Jan 1

ASJC Scopus subject areas

Engineering(all)
Physical and Theoretical Chemistry

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10.1021/j100248a032

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Dimerization rate of the 1-methyl-4-tert-butylpyridinyl radical and the photochemical process of the dimer cleavage. Kinetic and time-resolved ESR studies. / Akiyama, Kimio; Tero-Kubota, Shozo; Ikegami, Yusaku; Ikenoue, Tsuneo.

In: Journal of physical chemistry, Vol. 89, No. 2, 01.01.1985, p. 339-342.

Research output: Contribution to journal › Article › peer-review

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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.",

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N2 - 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.

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

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