Phototransformations of methylsubstituted oxiranes’ radical cations in freonic matrices at 77 K

Abstract

It has been established that, upon X-ray irradiation of various methyloxiranes in freonic matrices at 77 K, both open and cyclic (with the elongated C-C bond) forms of radical cations are stabilized. It has been shown that observed reversible photoinduced transformations of 2,3-dimethyloxirane and methyloxirane radical cations are related to the conversion between the open and cyclic forms of the radical cations with high quantum yields (0.02–0.39, depending on the oxirane and the matrix). For the trimethyloxirane radical cation the action of light on the trans-isomer of the open form results in its photoinduced transformation into a C-centered radical with low quantum efficiency (∼4 × 10−3). Tetramethyloxirane radical cations, stabilized in their open form, are resistant to the action of light. Probable causes of the observed effects are discussed. Upon the X-ray irradiation of 2,2-dimethyloxirane in freonic matrices at 77 K, a cyclic form of the radical cation is stabilized (presumably, as part of a complex with matrix molecules) which transforms into a distonic C-centered radical cation under the action of light with the quantum yield of ∼10−3.