Fluorinated ZnII Porphyrins for Dye-Sensitized Aqueous Photoelectrosynthetic Cells.

Three perfluorinated ZnII porphyrins were evaluated as n-type sensitizers in photoelectrosynthetic cells for HBr and water splitting. All the dyes are featured by the presence of pentafluorophenyl electron-withdrawing groups to increase the ground-state oxidation potential and differ for the nature and position of the π-conjugate linker between the core and anchoring group tasked to bind the metal oxide, in order to assess the best way of coupling with the semiconductor. A phenyl-triazole moiety was used to link the carboxylic anchoring group onto the meso position, while an ethynyl-phenyl linker was chosen to bridge carboxylic and cyanoacrylic groups onto the β-pyrrolic position. A combination of electrochemical, computational, and spectroscopic investigations confirmed the strong electron-withdrawing effect of the perfluorinated porphyrin core, which assures all the investigated dyes of the high oxidation potential required to the coupling with water oxidation catalysts (WOC). Such an electron-poor core, however, affects the charge separation character of the dyes, as demonstrated by the spatial distribution of the excited states, leading to a nonquantitative charge injection, although tilting of the molecules on the semiconductor surface could bring the porphyrin ring closer to the semiconductor, offering additional charge-transfer pathways. Indeed, all the dyes demonstrated successful in the splitting of both aqueous HBr and water, with the best results found for the SnO2/TiO2 photoanode sensitized with the β-substituted porphyrin equipped with a cyanoacrylic terminal group, achieving 0.4 and 0.1 mA/cm2 photoanodic currents in HBr and water under visible light, respectively. The faradaic yield for oxygen evolution in the presence of an IrIV catalyst was over 95%, and the photoanode operation was stable for more than 1000 s. Thus, the perfluorinated porphyrins with a cyanoacrylic anchoring group at the β-position should be considered for further development to improve the charge-transfer character.