Photophysics and photochemistry of the EE and ZE isomers of 1-(n-pyridyl)-4-phenyl-1,3-butadiene (n = 2, 3 and 4)

Abstract

The positional isomers of 1-(n-pyridyl)-4-phenyl-1,3-butadiene (n = 2, 3 and 4) have been synthesized in the EE and ZE geometries by common routes and characterized by spectrometric techniques. Their excited state properties were investigated by stationary and pulsed fluorimetric techniques and by laser flash photolysis. This paper reports the spectral, photophysical and photochemical behaviour of the EE and ZE isomers in a non-polar solvent. The photoisomerization proceeds through singlet, diabatic and/or adiabatic mechanisms with generally low quantum yield, owing to the role of internal conversion (markedly more important for n = 2). The role of intramolecular hydrogen bonds on the excited state properties of the ZE isomer of the 2-pyridyl derivative is particularly described.