Photophysical properties and singlet oxygen generation of three sets of halogenated corroles.

The luminescence, excited-state absorption, and singlet oxygen generation measurements were performed on three kinds of halogenated corroles: monohydroxyl halogenated corroles (Corrole-F, Corrole-Cl, Corrole-I), peripherally fluorine-substituted corroles (F0, F5, F10, F15), and gallium complexes (F10-Ga, F15-Ga). The fluorescence intensities progressively decrease whereas the triplet quantum yields, oxygen quenching rates, and singlet oxygen quantum yields increase with the increasing of the monohydroxyl halogen atomic weight. Replacing hydrogen atoms of meso-phenyl groups with fluorine atoms induces the blue-shifts of the emission spectra, higher triplet quantum yield, and smaller oxygen quenching rates. Of all peripherally fluorine-substituted corroles, F10 exhibited the highest singlet oxygen quantum yield. In comparison with the free base corroles, both gallium corrole complexes display much stronger fluorescence with the large blue-shifts of emission peaks and slightly higher triplet quantum yields but smaller oxygen quenching rates and singlet oxygen quantum yields. The reasons for the different photophysical behaviors of these corroles are discussed.