A2B type copper(III)corroles containing zero-to-five fluorine atoms: Synthesis, electronic structure and facile modulation of electrocatalyzed hydrogen evolution

Four low symmetric A2B meso-substituted Cu(III)corroles with electron withdrawing meso-aryl rings have been synthesized and characterized. A detailed analysis of the optical and redox properties has been carried out by comparing their optical spectroscopy, electrochemistry and spectroelectrochemistry to a series of DFT and TD-DFT calculations. A series of experiments demonstrate that these Cu(III)corroles can be used as highly effective catalysts for hydrogen evolution reactions (HERs). Moreover, when the number of fluorine atoms at B meso-position is increased, there is a marked enhancement in the catalytic ability of the corrole complexes, which demonstrates that modification to the structures of low symmetry corroles is a useful strategy for developing new HER catalysts.