Photophysical Efficiency Factors of Singlet Oxygen Generation from Core-modified Trithiasapphyrin Derivatives

The photophysical properties and the singlet oxygen generation efficiencies of meso-tetraphenyl-trithiasapphyrin $(S_3TPS)$ and meso-tetmkis(p-methoxy phenyl)-trithiasapphy rin ((p-MeO)-$S_3TPS$) have been investigated, utilizing steady-state and time-resolved spectroscopic methods to elucidate the possibility of their use as photosensitizers for photodynamic therapy (PDT). The observed photophysical properties were compared with those of other porphyrin-like photosensitizers in geometrical and electronic structural aspects, such as extended ${\pi}$ conjugation, structural distortion, and internal heavy atoms. The steady-state electronic absorption and fluorescence spectra were both red-shifted due to the extended ${\pi}$-conjugation. The fluorescence quantum yields were measured as very small. Even though intersystem crossing rates were expected to increase due to the increment of spin orbital coupling, the triplet quantum yields were measured as less than 0.15. Such characteristics can be ascribed to the more enhanced internal conversion rates compared with the intersystem crossing rates. Furthermore, the triplet state lifetimes were shortened to -1.0 ${\mu}s$ as expected. Therefore, the singlet oxygen quantum yields were estimated to be near zero due to the fast triplet state decay rates and the inefficient energy transfer to the oxygen molecule as well as the low triplet quantum yields. The low efficiencies of energy transfer to the oxygen molecule can be attributed to the lower oxidation potential and/or the energetically low lying triplet state. Such photophysical factors should be carefully evaluated as potential photosensitizers that have extended ${\pi}$-conjugation and heavy core atoms synthesized for red-shifted absorption and high triplet state quantum yields.