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.

Size and Electronic Effects on the Performance of (Corrolato)cobalt-Modified Electrodes for Oxygen Reduction Reaction Catalysis.

Considering the worldwide efforts for designing catalysts that are not based on platinum group metals while still reserving the many advantages thereof, this study focused on the many variables that dictate the performance of cathodes used for fuel cells, regarding the efficient and selective reduction of oxygen to water. This was done by investigating two kinds of porous carbon electrodes, modified by molecular cobalt(III) complexes chelated by corroles that differ very much in size and electron-withdrawing capability. Examination of the electronic effect uncovered shifts in the CoII/CoIII redox potentials and also large differences in the affinity of the cobalt center to external ligands. Spontaneous absorption of the catalysts was found to depend on the size of the corrole's substituents (C6F5 ≫ CF3 ≫ H) and the metal's axial ligands (PPh3 versus pyridine), as well as on the porosity of the carbon electrodes (BP2000 > Vulcan). The better-performing cobalt-based catalysts were almost as active and selective as 20% platinum on Vulcan in terms of the onset potential and the only 2-10% undesirable formation of hydrogen peroxide. Durability was also addressed by using the best-performing modified cathode in a proper anion-exchange membrane fuel cell setup, revealing very little voltage change during 12 h of operation.