Solid-supported perfluorinated phthalocyanine photosensitizers: Synthesis and singlet oxygen reactivity

The octakis-(iso-perfluoropropyl)octakis-fluoro zinc phthalocyanine (F[Formula: see text]PcZn) photosensitizer was supported on SiO 2 and TiO 2 via solution deposition. According to XPS, UV-vis, and TGA, F[Formula: see text]PcZn was adsorbed onto the surfaces of the metal oxides in the non-associated ˜monomolecular form via non-specific dispersive interactions. The solid-supported F[Formula: see text]PcZn materials were tested in photo degradation of methyl orange, a diazo dye, which occurred due to the production of reactive oxygen species (ROS). The related solid-supported materials containing H[Formula: see text]PcZn and F[Formula: see text]PcZn were also used to evaluate the effects of fluorine accretion from 0 to 64 while maintaining the same metal macrocycle platform. Reactivity studies using variable light excitation wavelengths revealed that the photo activities of the F[Formula: see text]PcZn and TiO 2 components of the dual, panchromatic F[Formula: see text]PcZn∪TiO 2 catalyst were mechanistically distinct and kinetically decoupled. The X[Formula: see text]PcZn∪oxides materials, X [Formula: see text] H, F, were less active and less stable than F[Formula: see text]PcZn-containing ones. Due to the presence of bulky perfluorinated groups and the absence of C-H bonds, F[Formula: see text]PcZn produced chemically robust and thermally stable, solid-supported photosensitizer materials capable of generating ROS without self-degradation.