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Singlet oxygen-mediated oxidation of sulfides with palladium(II) porphyrinates: The effect of partly conjugated peripheral substituents
Oxidation of sulfides by singlet oxygen has been extensively studied, yet the structure-photoactivity relationship of these photosensitizers remains underinvestigated. In the present work the photocatalytic performance of a set of functionalized palladium(II) porphyrinates was comprehensively investigated in the photocatalytic oxidation of sulfides to reveal mutual influence of structural peculiarities onto the photosensitizing properties. The photophysical properties of these compounds, including stationary concentration of singlet oxygen in solution, were also studied. These findings allowed to track the influence of tunable partial conjugation of meso-substituents on the overall catalytic performance. In addition, the values of singlet oxygen quantum yields were determined and their correlations with reaction rates were observed. A kinetic model was proposed to explain the relation between the value of singlet oxygen quantum yield and sulfoxidation rate.