High pressure luminescence studies of metalloporphyrins in polymeric media

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Abstract
High pressureluminescencemeasurements have been made on free base tetraphenylporphyrin (H2–TPP), as well as on Zn–TPP, Mg–TPP, Cr–TPP, and Cu–octaethylporphyrin (Cu–OEP), in PMMA and PS. In the case of H2–TPP, Zn–TPP, and Mg–TPP the efficiency of fluorescence and phosphorescence (Zn–TPP) was pressure dependent as was the relative energy of the excited singlet and triplet states. The relative transfer rates have been calculated, and it was shown that the fluorescence efficiency is limited by intersystem crossing while the phosphorescence efficiency is limited by both radiationless rates S 1→T 1 and T 1→S 0. The rate S 1→T 1 scaled very well with the S 1–T 1 energy difference, and the rate T 1→S 0 with the T 1–S 0 energy difference. In the case of Cu–OEP and Cr–TPP only phosphorescence was observed from two states. At low pressurephosphorescence comes mainly from the high energy excited state (2 T 1), while at high pressures it comes from the low energy excited state (4 T 1). The excitation maximum was found to be strongly dependent on pressure. The large red shift of the excitation maximum causes changes in the feeding of 2 T 1 and 4 T 1 states, which result in an apparent increase of the radiative rates. Some experimental results on three phthalocyanines are also briefly presented and discussed.

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