Electron-withdrawing perfluoroalkyl peripheral groups grafted on phthalocyanine (Pc) macrocycles improve their single-site isolation, solubility, and resistance to self-oxidation, all beneficial features for catalytic applications. A high degree of fluorination also enhances the reducibility of Pcs and could alter their singlet oxygen (¹O₂) photoproduction. The ethanol/toluene 20:80 vol % solvent mixture was found to dissolve perfluorinated F_nPcZn complexes, n = 16, 52, and 64, and minimize the aggregation of the sterically unencumbered F₁₆PcZn. The ¹O₂ production ability of F_nPcZn complexes was examined using 9,10-dimethylanthracene (DMA) and 2,2,6,6-tetramethylpiperidine (TEMP) in combination with UV-vis and electron paramagnetic resonance (EPR) spectroscopy, respectively. While the photoreduction of F₅₂PcZn and F₆₄PcZn in the presence of redox-active TEMP lowered ¹O₂ production, DMA was a suitable ¹O₂ trap for ranking the complexes. The solution reactivity was complemented by solid-state studies via the construction of photoelectrochemical sensors based on TiO₂-supported F_nPcZn, F_nPcZn|TiO₂. Phenol photo-oxidation by ¹O₂, followed by its electrochemical reduction, defines a redox cycle, the ¹O₂ production having been found to depend on the value of n and structural features of the supported complexes. Consistent with solution studies, F₅₂PcZn was found to be the most efficient ¹O₂ generator. The insights on reactivity testing and structural-activity relationships obtained may be useful for designing efficient and robust sensors and for other ¹O₂-related applications of F_nPcZn.

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