Methylthiophenyl- and Methylthiobiphenyl-Substituted A₂B Co^IIIcorroles: Modulating Electrocatalyzed Hydrogen...

Four A₂B-type Co^IIIcorroles (2a-2d) with electron-donating/withdrawing substituents at the A₂ meso-aryl substituents and a 4-(methylthio)phenyl ring at the B position have been synthesized and characterized, along with a series of meso-extended Co^IIIcorroles (4a-4c) with 4'-(methylthio)biphenyl moieties. The electronic structures and structure-property relationships of the dyes have been analyzed by comparing their redox and optical properties to trends predicted in density functional theory calculations. Au electrodes surface-modified with 2a-2d and 4a-4c are highly efficient catalysts for electrocatalyzed hydrogen evolution reactions, and the electrocatalytic properties can be readily modulated by fine-tuning the electronic structure of the Co^IIIcorrole and the distance between the "Au-S" bond and Co^III center.