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Formation of distonic dimer radical cations, characterised by spatially separated charge and radical site, was observed in our previous studies with irradiated frozen Freon matrices containing vinyl ethers, 2,3-dihydrofuran (2,3-DHF) 2,3] and 2,3-dihydropyran 4J. Investigation of the transformations of dimer radical cations may be of general interest for elucidating mechanism of the radiation-induced polymerisation, as demonstrated before in the case of homopolymerisation of alkylmaleimides 5]. 2,3- DHF is known to polymerise - similarly as other vinyl ethers - by a cationic mechanism. Role of the distonic dimer radical cation of 2,3-DHF as a possible initiator of radical polymerisation was investigated now, applying both the low-temperature EPR spectroscopy and quantum chemical methods.