Coupling between tautomerism and radiationless deactivation in porphycenes

Abstract

Abstract Quantum yields of fluorescence of porphycenes – porphyrin isomers – can vary by orders of magnitude, even for very similar derivatives, such as meso-dimethyl- vs. meso-tetramethylporphycene. In weakly emitting porphycenes the fluorescence intensity strongly depends on viscosity and can be recovered by placing a molecule in a rigid environment. We postulate that the efficient nonradiative deactivation is due to the quantum effect, delocalization of the inner protons. The delocalization, which increases with the strength of intramolecular hydrogen bonds may induce structural changes that lead to distortion from planarity and, as a result, efficient S0 ← S1 internal conversion. The effect seems to be general, as indicated by good correlation between the quantum yield of fluorescence and the distance between H-bonded nitrogen atoms, the latter being a reliable measure of hydrogen bonding strength. Based on the available photophysical and X-ray data, such correlation was found so far for over 20 differently substituted porphycenes.