Electron spin resonance observations on trapped electrons and free radicals formed in olefins at 77 °K by γ-irradiation

Electron spin resonance (e.s.r.) methods have been used to search for the γ-ray-induced formation of trapped electrons and free radicals in 13 straight-chain and branched-chain terminal olefins at 77 °K. When e.s.r. spectra were observed they were used to identify the species present. Changes induced by subsequent exposure to visible and ultraviolet (u.v.) light were investigated. Trapped electrons were observed in three olefins that exist as glasses at 77 °K, hexene-1, hexene-2, and 2-methylbutene-1, but were not detected in two other glassy olefins, possibly because of rapid annealing. No trapped electrons were found in polycrystalline olefins at 77 °K. The possibility that CO2− ions have been misinterpreted as trapped electrons in these and other systems is discussed and eliminated. The formation and behavior of free radicals and trapped electrons in irradiated 2-methylbutene-1 are analogous to those previously reported for 2-methylpentene-1 under similar conditions. These observations support the hypothesis that in these two systems ions produced initially isomerize rapidly, leading to the formation of the free radicals detected by e.s.r. The results of a subsidiary experiment suggest that hydrogen abstraction from the matrix is induced by u.v. photolysis of the radicals present in 2-methylpentene-1.