On the origin of radiationless transitions in porphycenes.

A model for the radiationless deactivation of porphycenes has been proposed based on the theoretical prediction that the lowest electronic state of one of the cis tautomeric forms corresponds to an open-shell nonplanar structure. The radiationless channel is provided by crossing of the potential energy surfaces of the ground and lowest excited states along the hydrogen-transfer coordinate. The model explains the large dependence of fluorescence of several porphycenes on viscosity. It also allows prediction of the emissive properties for differently substituted porphycenes.