The photoprocesses of a series of N-substituted dibenzb,fazepines (iminostilbenes) were studied by absorption and emission spectroscopy, by laser flash photolysis, and by preparative irradiation with NMR analysis. In solutions, 2pi+2pi photodimers of N-cyano and N-acyl dibenzazepines are formed via the triplet state upon acetone- or benzophenone-sensitized energy transfer. T-T absorption spectra were measured and absorption coefficients were determined. The triplet energy transfer is equally efficient for N-alkyl dibenzazepines, which do not dimerize. Excited states of npi character in the latter cases are discussed to rationalize the different reactivities. In spite of negligible intersystem crossing of 2.1 dibenzazepine derivatives, photodimers of N-acyl and N-cyano dibenzazepines are formed upon direct excitation in concentrated solutions (0-01-0.1 mol dm(-3)) as well as in the solid state. A selective anti-configuration of the photodimers was found throughout. References: 34
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