Conformer-specific and two-fold adiabatic photoisomerization of ZZ-1,4-di-(2-quinolylethenyl)benzene

Abstract

Irradiation of the ZZ stereoisomer of 1,4-di-(2′-quinolylethenyl)-benzene was found to cause direct adiabatic (one photon–two bond) isomerization to a product having the same lifetime as the EE isomer but a rather different spectrum with respect to that obtained by direct excitation of the EE one. To clarify this unexpected behaviour, the conformational equilibria of the EE stereoisomer have been studied in non-polar solvent by fluorimetry. The most abundant conformers, formed by the hindered rotation of the condensed-ring groups around the quasi-single bond with the ethenic carbons, have been characterized by the selective effect of the excitation energy on the fluorescence spectrum. The combined application of the principal component analysis allowed the separation of the spectral properties of three conformers to be achieved. Information on their structures was obtained by theoretical calculations. The results of the present conformational study clearly indicated that the fluorescence spectrum of the photoproduct of ZZ belongs to a specific component of the conformer mixture of the EE isomer.