Photobehavior of the Geometrical Isomers of Two 1,4-Distyrylbenzene Analogues with Side Groups of Different Electron Donor/Acceptor Character

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2010-10, Vol.114 (40), p.10761-10768
• Main Authors: Ciorba, S, Galiazzo, G, Mazzucato, U, Spalletti, A
• Format: Article
• Language: English
• Subjects: A: Dynamics, Clusters, Excited States
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp105383e

The photobehavior of two 1,4-distyrylbenzene analogues where the central benzene ring is asymmetrically substituted with a pyrid-4-ylethenyl group at one side and thien-2-ylethenyl or a p-nitrostyryl group at the other side, has been studied in two solvents at room temperature. The four geometrical isomers (EE, ZE, EZ, and ZZ) of each compound were separated by the combined use of HPLC and spectrophotometric techniques. The radiative/reactive competition in their excited state relaxation was particularly examined: the diabatic/adiabatic contributions were estimated and a reasonable interpretation of the photoisomerization mechanism was proposed. The role of the conformational isomers was also investigated by measured and computed spectral data. Since the different electron donor/acceptor character of the side groups of these molecules can induce charge transfer phenomena that can affect the relaxation pathways of their excited states, the photobehavior was compared in inert and polar solvents to clarify the role of the intramolecular charge transfer. The latter was found to affect markedly the relaxation properties and to induce interesting fluorosolvatochromic effects, particularly in the p-nitro derivative. The participation of the triplet state in the reaction mechanism of the latter was also investigated by flash photolysis and sensitized experiments.