Estimation of the Fraction of Spin-Correlated Radical Ion Pairs in Irradiated Alkanes using Magnetosensitive Recombination Luminescence from Exciplexes Generated upon Recombination of a Probe Pair

Anatoly R. Melnikov, Vladimir N. Verkhovlyuk, Evgeny V. Kalneus, Valeri V. Korolev, Vsevolod I. Borovkov, Peter S. Sherin, Maria P. Davydova, Sergei F. Vasilevsky, Dmitri V. Stass

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5 Citations (Scopus)

Abstract

We suggest a convenient probe exciplex system for studies in radiation spin chemistry based on a novel acceptor-substituted diphenylacetylene, 1-(phenylethynyl)-4-(trifluoromethyl)benzene that has a very short fluorescence lifetime (<200 ps) and low quantum yield (0.01) of intrinsic emission, provides efficient electron capture in alkanes and efficient exciplex formation upon recombination in pair with DMA radical cation, while exhibiting a shifted to red exciplex emission band as compared to the parent system DMA-diphenylacetylene. After chemical, luminescent, radiation and spin-chemical characterization of the new system we used the magnitude of magnetic field effect in its exciplex emission band for experimental estimation of the fraction of spin-correlated radical ion pairs under X-irradiation with upper energy cutoff 40 keV in a set of 11 alkanes. For linear and branched alkanes magnetic field effects and the corresponding fractions are approximately 19-20% and 0.28, while for cyclic alkanes they are lower at 16-17% and 0.22, respectively.

Original languageEnglish
Pages (from-to)239-267
Number of pages29
JournalZeitschrift fur Physikalische Chemie
Volume231
Issue number2
DOIs
Publication statusPublished - 1 Feb 2017

Keywords

  • Diphenylacetylene
  • exciplex luminescence
  • magnetic field effect
  • radical ion pair
  • spin correlation
  • X-ray irradiation

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