Photoisomerization and Photocyclization Reactions of 1-Styrylanthracene

On triplet sensitization, 1-styrylanthracene (1SA) undergoes adiabatic cis → trans one-way isomerization (3c* → 3t*) similarly to 2-anthrylethylenes. However, upon direct irradiation, cis-1SA in the singlet excited state mostly undergoes cyclization to a dihydrophenanthrene-type product (DHP), 4a,4b-dihydrobenzo[b]chrysene, competing with an inefficient intersystem crossing to 3c* followed by one-way isomerization. The produced DHP, in deaerated benzene, is reverted to cis-1SA by a thermal (Ea = 14.9 kcal mol−1) or a photochemical pathway; however, under an oxygenated atmosphere DHP gives benzo[b]chrysene. A failure in the production of a cyclized product upon the excitation of trans-1SA shows that the isomerization really takes place in a one-way fashion.

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