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Photochemistry of Oxirane-Derived Radical Cations in Freonic Matrices at 77 K

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Moscow University Chemistry Bulletin Aims and scope

Abstract

The data on the structure and the features of the photochemical reactions for radical cations (RCs) derived from various oxiranes (epoxides) that can be stabilized in Freon matrices at 77 K are summarized. The nature of the RCs and the products of their photochemical transformations have been determined via quantum chemistry, electron paramagnetic resonance (EPR) and low-temperature UV/Vis spectroscopy. For the RCs, it is shown that, depending on the structure of the precursor molecule, transitions between their ring-open and ring-closed forms, deprotonation reactions affording C-centered radicals and more complex transformations can take place when exposed to light. Possible explanations of the observed effects are discussed.

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Notes

  1. The paramagnetic centers formed upon the X-ray irradiation of cis- and trans-2,3-DMO/Freons solutions at 77 K (detected via EPR and UV/Vis spectroscopy) as well as the character of their mutual thermally induced and photochemical transformations are identical. Further on we will not specify whether cis- or trans-isomers were used since the obtained results were identical for those two substrates.

  2. At the edges of the EPR spectra, there are additional low-intensity components of multiplet EPR signals, not clearly seen in Figs. 3 or 5. These can be seen at higher gains.

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Funding

This work has been performed with financial support granted by the Russian Foundation for Basic Research (project 19-03-00015) with the use of equipment purchased on behalf of the Development Program of Moscow State University. Calculations have been performed using the resources of the Supercomputing Center of Moscow State University [29].

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Authors and Affiliations

  1. Department of Chemistry, Moscow State University, 119991, Moscow, Russia

    M. Ya. Melnikov, I. D. Sorokin, O. I. Gromov, V. I. Pergushov & D. A. Pomogailo

  2. Russian Institute for Scientific and Technical Information, 125190, Moscow, Russia

    D. A. Pomogailo

Authors
  1. M. Ya. Melnikov
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  2. I. D. Sorokin
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  3. O. I. Gromov
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  4. V. I. Pergushov
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  5. D. A. Pomogailo
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Correspondence to M. Ya. Melnikov.

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Melnikov, M.Y., Sorokin, I.D., Gromov, O.I. et al. Photochemistry of Oxirane-Derived Radical Cations in Freonic Matrices at 77 K. Moscow Univ. Chem. Bull. 76, 1–13 (2021). https://doi.org/10.3103/S0027131421010089

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  • DOI: https://doi.org/10.3103/S0027131421010089

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