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Abstract Photoredox catalysis has proven to be a powerful tool in synthetic organic chemistry. The rational design of photosensitizers with improved photocatalytic performance constitutes a major advancement in photoredox organic transformations. This review summarizes the fundamental ground-state and excited-state photophysical and electrochemical attributes of molecular photosensitizers, which are important determinants of their photocatalytic reactivity. 

A cobalt porphyrin molecule, namely CoTcPP (TcPP = the dianion of meso -tetra(4-carboxyphenyl)porphyrin), is intercalated into zirconium phosphate (ZrP) layers as an effective way to heterogenize a porphyrin-based molecular electrocatalyst. Fourier-transform infrared (FT-IR) spectroscopy, X-ray powder diffraction (XRPD) measurements, UV-Vis spectroscopy, elemental mapping, energy dispersive X-ray (EDX) analysis, inductively coupled plasma mass spectrometry (ICP-MS) and X-ray photoelectron spectroscopy (XPS) were utilized to determine the successful intercalation of CoTcPP into ZrP. While the CoTcPP molecule is not amendable to be used as a heterogeneous catalyst in basic environment due to the carboxylic groups, the intercalated species (CoTcPP/ZrP) is effective towards water oxidation from KOH aqueous solution when utilized as a heterogeneous electrocatalyst and shows remarkable catalytic durability. Electrochemical results show that CoTcPP/ZrP requires an overpotential of 0.467 V to achieve a current density of 10 mA cm −2 while the pristine α-ZrP shows negligible electrocatalytic OER behavior. 

In this work, we describe bis-cyclometalated iridium complexes with efficient deep-red luminescence. Two different cyclometalating (C^N) ligands-1-phenylisoquinoline (piq) and 2-(2-pyridyl)benzothiophene (btp)-are used with five strong π-donating ancillary ligands (L^X) to furnish a suite of nine new complexes with the general formula Ir(C^N) 2 (L^X). Improvements in deep-red photoluminescence quantum yields were accomplished by the incorporation of sterically encumbering substituents onto the ancillary ligand, which can enhance the radiative rate constant ( k r ) and/or reduce the non-radiative rate constant ( k nr ). Five of the complexes were characterized by X-ray crystallography, and all of them were investigated by in-depth spectroscopic and electrochemical measurements. 

Free-basemeso-tetra(pentafluorophenyl)porphyrin,1, is electrocatalytically active for hydrogen gas generation in the presence ofp-toluenesulfonic acid.