Effect of the positional isomerism on the photoreactivity of styryloxazoles

Abstract

Abstract This paper describes the results obtained in the study of the photobehaviour of heteroanalogs of stilbene bearing an oxazole ring. The competitive relaxation processes (fluorescence, isomerization and cyclization) of the excited states of n-styryloxazoles (n = 2 and 4) were investigated and compared with the behaviour previously reported for n = 5. After preparation of the unknown compound with n = 4 and of its positional isomer with n = 2 (the latter with a new method of synthesis), their photobehaviour was firstly investigated in preparative conditions by NMR analysis to measure the chemical yields of their photoproducts. The study was then continued in mild irradiation conditions to measure the quantum yields of the competitive photoreactions in the primary irradiation steps. The effects of the position of the styryl group at the oxazole ring, the relative abundance of the various conformers and the possible formation of intramolecular H bonds on the deactivation pathways are described. Quantum-mechanical Hyperchem calculations proved to be very useful to describe the conformational equilibria and the role of conformers on photoreactivity while more refined DFT calculations on the Z isomers allowed to explain the structure dependent competition between their isomerization/cyclization processes. The effect of the replacement of the phenyl ring with a second heteroaromatic group of electron donor character was investigated for the 5-(2-(furan-2-yl) ethenyl) oxazole.