Wiley InterScience Backfile Collection 1832-2000
Chemistry and Pharmacology
Direct and Sensitized Photoisomerization of α,δ-PhenylfulgidesThe photoreactions starting from the E- and E-E-isomers of mono-, di-, tri- and tetra-(substituted-)phenylfulgides are investigated. The phenylfulgides show strong steric interactions in the molecular framework. For that reason internal conversion is the main deactivation process which increases in the series of mono-, tri- and tetraphenylfulgides. The α,δ-di-(substituted-)-phenylfulgides show the highest photoreactivity. At room temperature in no case luminescence is observed from any E(E-E)-, Z(E-Z, Z-E)- or Z-Z-phenylfulgid isomer of the substances under study. Intersystem crossing cannot compete neither with thermal deactivation nor can it be observed by applying both the internal and external heavy atom effect. The phenylfulgides show typical ππ*-photoreactivity: in the singlet state E-Z-isomerization about one double bond competes with electrocyclic ring closure; in the triplet state only simultaneous E-Z-isomerization about the two double bonds is observed. The steric and electronic substituent influences on the photoreactivity are interpreted. A first qualitative model of the isomerization reactions of the fulgides in the excited states is established.
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