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

Pallas Chou; Lauren Kim; Sammer M Marzouk; Rui Sun; Alaina C Hartnett; Dilek K Dogutan; Shao-Liang Zheng; Daniel G Nocera

doi:10.1021/acsomega.2c00109

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

ACS Omega. 2022 Mar 2;7(10):8988-8994. doi: 10.1021/acsomega.2c00109. eCollection 2022 Mar 15.

Authors

Pallas Chou¹, Lauren Kim¹, Sammer M Marzouk¹, Rui Sun¹, Alaina C Hartnett¹, Dilek K Dogutan¹, Shao-Liang Zheng¹, Daniel G Nocera¹

Affiliation

¹ Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge, Massachusetts 02138, United States.

Abstract

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 k _app = 5.79 ± 0.47 × 10³ M^-1 s^-1.