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Electron paramagnetic resonance (EPR) study of γ-radiation-induced radicals in 1,3,5-trithiane and its derivatives

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Abstract

Radicals formed in γ-irradiated 1,3,5-trithiane (TT) and its three derivatives, α- and β-2,4,6-trimethyl-1,3,5-trithiane (α-TMT and β-TMT), and 2,4,6-trimethyl-2,4,6-triphenyl-1,3,5-trithiane (TMTPT), were studied by the electron paramagnetic resonance (EPR) method in the solid state. The sulfur radical cations (>S+•) were identified in all compounds at 77 K. In TT and its two derivatives, α-TMT and β-TMT, the >S+• decay via deprotonation-forming C-centered radicals. Further increase of temperature up to 293 K results in the appearance of thiyl-type radicals (RS•). In TMTPT, the >S+• are stable up to 250 K. They formed the intermolecularly three-electron-bonded dimeric radical cations (S∴S)+ while RS• radicals were not observed. Some of the radical assignments and their EPR parameters (g and a hyperfine splittings) obtained support from the DFT calculations.

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Acknowledgment

We would like to thank the Faculty of Chemistry in Adam Mickiewicz University (E.J.B., B.M.) and the Institute of Nuclear Chemistry (G.S., K.B.) for financial support. This work was partly supported by the Office of Basic Energy Sciences of the U.S. Department of Energy (I.C.). This paper is Document No. NDRL-4801 from the Notre Dame Radiation Laboratory.

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Authors and Affiliations

  1. Institute of Nuclear Chemistry and Technology, 03-195, Warsaw, Poland

    Grazyna Strzelczak & Krzysztof Bobrowski

  2. Faculty of Chemistry, Adam Mickiewicz University, 60-780, Poznan, Poland

    Edyta Janeba-Bartoszewicz & Bronislaw Marciniak

  3. Radiation Laboratory, University of Notre Dame, Notre Dame, Indiana, 46556, USA

    Ian Carmichael

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  1. Grazyna Strzelczak
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  2. Edyta Janeba-Bartoszewicz
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  3. Ian Carmichael
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  4. Bronislaw Marciniak
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  5. Krzysztof Bobrowski
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Correspondence to Grazyna Strzelczak.

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Strzelczak, G., Janeba-Bartoszewicz, E., Carmichael, I. et al. Electron paramagnetic resonance (EPR) study of γ-radiation-induced radicals in 1,3,5-trithiane and its derivatives. Res Chem Intermed 35, 507–517 (2009). https://doi.org/10.1007/s11164-009-0054-4

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