I. D. Sorokin, O. I. Gromov, V. I. Pergushov, D. A. Pomogailo, M. Ya. Melnikov, “Effect of Freon matrices on the intermediates stabilized in X-ray irradiated 1,7-dioxaspiro[5,5]undecane solutions at 77K”, Mendeleev Commun., 2021, Volume 31, Issue 3,Pages <nobr>343

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Communications

Effect of Freon matrices on the intermediates stabilized in X-ray irradiated 1,7-dioxaspiro[5,5]undecane solutions at 77K

I. D. Sorokin^a, O. I. Gromov^a, V. I. Pergushov^a, D. A. Pomogailo^ab, M. Ya. Melnikov^a

^a Department of Chemistry, M.V. Lomonosov Moscow State University, Moscow, Russian Federation
^b Russian Institute for Scientific and Technical Information, Russian Academy of Sciences, Moscow, Russian Federation

Abstract: Freon matrices affected the nature of species stabilized upon the X-ray irradiation of frozen 1,7-dioxaspiro[5,5]undecane (DOSU)/CF₃CCl₃ or DOSU/CFCl₃ solutions at 77K. This manifested in the stabilization of a ring-closed DOSU radical cation (RC) with an absorption maximum at ∼440nm in CF₃CCl₃ versus a paramagnetic intermediate with no absorption in this spectral region and a notably different EPR spectrum in CFCl₃. Interestingly, the ultimate product in a sequence of photochemical and thermally induced transformations was the same in both matrices: a distonic DOSU RC with a terminal alkyl fragment afforded upon C–C bond cleavage at the spiro carbon atom.

Keywords: 1,7-dioxaspiro[5,5]undecane, radical cations, EPR spectroscopy, UV/VIS spectroscopy, DFT, photochemistry, reactive intermediates, matrix stabilization, Freons, matrix effect.

Language: English

DOI: 10.1016/j.mencom.2021.04.020