Substituent Effects of Porphyrin on Singlet Oxygen Generation Quantum Yields

ABSTRACT

The singlet oxygen photosensitizing efficiencies of the ortho-, meta-, and para-substituted free-base and zinc (II) tetraarylporphyrins have been investigated on the basis of the heavy atom effect, electronegativity, and spatial orbital overlap. Both the endocyclic and exocyclic heavy atom effects have been exploited to induce various degrees of spin-orbit coupling. The ground state and the lowest singlet excited electronic state of the porphyrins have been studied using optical absorption and fluorescence emission spectroscopic techniques. The experimental data suggest that implementation of the halogen substituent effect to enhance the photosensitizing properties of a chromophore from the excited triplet state should be done cautiously, as it may have negative implications.