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Phosphorescence and Photophysical Parameters of Porphycene in Cryogenic Matrices

Matrix isolation studies were carried out for porphycene, an isomer of porphyrin, embedded in solid nitrogen and xenon. The external heavy atom effect resulted in nearly a 100% population of the triplet state and in the appearance of phosphorescence, with the origin located at 10163 cm−1. This energy is much lower than that corresponding to the T1 position in porphyrin. This difference could be explained by postulating that the orbital origin corresponds in both isomers to the second excited singlet state, which lies much closer to S1 in porphycene. Most of the vibrational frequencies observed in the phosphorescence spectrum correspond to totally symmetric modes, but several ones were assigned to the out-of-plane Bg vibrations. These bands are not observed in fluorescence, which suggests their possible role in vibronic-spin-orbit coupling.