Photochemical Rearrangements of C6H8, C7H10, and C8H12 Radical Cations in Solid Argon at 20 K

Article abstract of DOI:10.1021/j150657a011

C6H8 radical cations have been produced by matrix photoionization techniques and trapped in solid argon.Electronic spectra show that two different types of products are formed; a conjugated diene cation with strong and weak absorption between 30000 and 20000 cm^-1 and conjugated triene cations with a strong absorption between 28000 and 22000 cm^-1 and weak absorptions between 18000 and 14000 cm^-1.With selective photolysis in the high-energy bands, the conjugated triene cation geometric isomers were interconverted while the cyclic diene cations were ring opened to give conjugated triene cations.Similar experiments with cyclic and bicyclic C7H10 cations gave three conjugated heptatriene cation conformers, and cyclic C8H12 cations yielded a number of conjugated octatriene cation isomers.