Structure of radicals produced by γ-radiolysis. Part 4. Adamantane matrices doped with various 5-membered heterocyclic molecules

The effects of γ-adiolysis at room temperature on adamantane and adamantane-d16 matrices doped with 5-membered heterocyclic molecules has been examined by X-band electron spin resonance (esr) spectrometry. Radical structures formed from heterocyclic solute molecules are discussed and tentative assignments made for 2-methyl-, 3-methyl-, and 2,5-dimethylthiophene, 2-methyl-, and 2,5-dimethylfuran. Discussion of possible radical structures derived from furan, tetrahydrofuran, 2-methyl- and 3-methyltetrahydrofuran, 2,5-dihydrofuran, and 4,5-dihydro-2-methylfuran, is included, but unambiguous assignments of structure cannot be made for these compounds from the esr data obtained. Other molecules examined included thiophene, pyrrole, and 1-methyl- and 1,2,5-trimethylpyrrole. For these latter molecules, experimentally obtained first derivative X-band esr spectra were too poorly resolved to allow rational discussion of possible structures. It was noted that perdeuterated adamantane matrices provided superior resolution for esr spectra derived from radicals with a delocalized spin center such as allyl or allenyl species.