Role of internal conversion on the excited state properties of trans-styrylpyridines Original Research Article

A theoretical and photophysical study of the three isomeric trans-n-styrylpyridines (n = 2,3,4) has been carried out to evaluate the role of internal conversion (IC) on their deactivation pathways from the singlet manifold. Calculations by the QCFF/PI and CNDO/S methods and application of current theories of radiationless transitions allowed the rate constants for IC to be evaluated. The fluorescence lifetimes measured in the picosecond region and the fluorescence and trans → cis photoisomerization quantum yields from previous works allowed the rate constants for the non-radiative and non-reactive deactivation processes to be calculated. The experimental results were in a reasonable agreement with the theoretical predictions on the role of IC (markedly more important for the 2 and 4 derivatives) and confirmed that intersystem crossing is a low efficiency process for these azastilbenes. On the basis of the temperature and the solvent viscosity effects on the electronic spectra, an interpretation of the excitation energy effect on the quantum yields of the 3 isomer was attempted.