Studies on the Novel and Highly-Efficient Chemical Reactions Using Pulse Radiolysis and Flash Photolysis Combined Method.

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By using pulse radiolysis and flash photolysis combined metods novel and highly efficient chemical reactions have been studied as described below ;(1) Photochemical reactions of aromatic radical cations. Unimolecular cis-trans isomerizations have been observed upon the photoirradiation of stilbene and diphenyl-1,3-butadiene radical cations. The lifetimes of the photoexcited states of aromatic radical cations have been estimated by the addition of hole transfer quencher such as anisole to be subnanosecond order. The correlation between the lifetimes and unimolecular reactivities of aromatic radical cations in the excited state was also observed.(2) Chemical reactivities of active species with a C=N group. Upon one-electron oxidation and reduction of nitrile ylid produced by photoirradiation novel active species was produced and the reactivity was investigated. Efficient reaction of biphenylyl ilid with carbon dioxide was found.(3) Chemical reactivity of organophosphorous compounds in the exicited state. Photochemical reactions of bis- or tris-aryl phosphate and phopsphonate resulted in intramolecular biaryl formation and aryl migration via excimer and monomer excited state, reapectively.