Surprising Route to a Monoazaporphyrin and Full Characterization of Its Complexes with Five Different 3d Metals

In the search for mild agents for the oxidative cyclization of tetrapyrromethane to the corresponding corrole, we discovered a route that leads to a monoazaporphyrin with three meso-CF₃ groups. Optimization studies that allowed access to appreciable amounts of this new macrocycle paved the way for the preparation of its cobalt, copper, nickel, zinc, and iron complexes. All complexes were fully characterized by various spectroscopic methods and X-ray crystallography. Their photophysical and electrochemical properties were determined and compared to those of analogous porphyrins in order to deduce the effect of the peripheral N atom. Considering the global efforts for designing efficient alternatives to platinum group metal (PGM) catalysts, they were also absorbed onto a porous carbon electrode material and studied as electrocatalysts for the oxygen reduction reaction (ORR). The cobalt complex was found to be operative at a quite positive catalytic onset potential and with good selectivity for the desirable 4-electrons/4-protons pathway.