Synthesis, Characterization, and Hydrogen Evolution Activity of Metallo-<i>meso</i>-(4-fluoro-2,6-dimethylphenyl)porphyrin Derivatives

Zn­(II), Cu­(II), and Ni­(II) 5,10,15,20-tetrakis­(4-fluoro-2,6-dimethylphenyl)­porphyrins (TFPs) have been synthesized and characterized. The electronic spectroscopy and cyclic voltammetry of these compounds, along with the free-base macrocycle (2H-TFP), have been determined; 2H-TFP was also structurally characterized by X-ray crystallography. The Cu­(II)­TFP exhibits catalytic activity for the hydrogen evolution reaction (HER). The analysis of linear sweep voltammograms shows that the HER reaction of Cu­(II)­TFP with benzoic acid is first-order in proton concentration with an average apparent rate constant for HER catalysis of kapp = 5.79 ± 0.47 × 103 M–1 s–1.