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Substituent‐Dependent Reactivity in the Photodimerization of N‐Substituted Dibenz[ b , f ]azepines
Author(s) -
Querner Jens,
Wolff Thomas,
Görner Helmut
Publication year - 2004
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200305199
Subject(s) - substituent , reactivity (psychology) , chemistry , medicinal chemistry , stereochemistry , medicine , alternative medicine , pathology
The photoprocesses of a series of N‐substituted dibenz[ b , f ]azepines (iminostilbenes) were studied by absorption and emission spectroscopy, by laser flash photolysis, and by preparative irradiation with NMR analysis. In solutions, 2π+2π 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 nπ* character in the latter cases are discussed to rationalize the different reactivities. In spite of negligible intersystem crossing of 21 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.