Approach to Biradical Chemistry utilizing Photoindeced Electron Transfer

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We studied the new generation and characterization of various biradicals generated in the photoinduced electron transfer reactions [(1)-(7) except for (6)] and a related direct irradiation reaction [(6)]. In the former, the keys step is a facile back electron transfer in a radical ion pair, which converts quantitatively the reactive radical cation intermediates to the corresponding diradicals.As results, we have found novel cation radicals and biradicals which undergo unprecedented reactions, and gained valuable insights into steric and electronic structures of controversial biradicals. The studies is still now in progress and thus, next year, we will apply a grant-in-aid to the Ministry of Education, Culture, Sports, Science, and Technology.(1) Photoinduced Electron Transfer Reactions of 2,2-Diaryl-1-methylenecyclopropane.(2) Photoinduced Electron Transfer Reactions of 5,5-Dimethyl-2,3-bis(α-styryl)-1,3-cyclobutadiene.(3) Photoinduced Electron Transfer Reactions of cis-and trans-2-Anisyl-3-methyl-1-methylenecyclopropane and cis-and trans-2-Anisyl-1-ethylidenecyclopropane.(4) Photoinduced Electron Transfer Reactions of 7-(Dianisylmethylene)-2,3-diazabicyclo[2.2.1]hept-2-ene.(5) Photoinduced Electron Transfer Reactions of 3,3-Dimethy1-4-methylene-2,2-bis(4-methoxyphenyl)cyclobutanone and 4-Isopropilidene-2-bis(4-methoxyphenyl)cyclobutanone.(6) Direct Irradiation reaction of 7-(Diarylmethylene)-2,3-diazabicyclo[2.2.1]hept-2-ene.(7) Photoinduced Electron Transfer Reactions of 1,2-Bis(α-styryl)benzenes and 3,4-bis(α-styryl)furans.