Computational Investigation into Heteroleptic Photoredox Catalysts Based on Nickel(II) Tris-Pyridinethiolate for Water Splitting Reactions

This work demonstrates a strategy to fine-tune the efficiency of photoredox water splitting Ni(II) tris-pyridinethiolate catalyst through heteroleptic ligand design using computational investigation catalytic mechanism. Density functional theory (DFT) calculations, supported by topology analyses quantum atoms in molecules (QTAIM), show that introduction electron donating (ED) −CH3 and withdrawing (EW) −CF3 groups on thiopyridyl (PyS–) ligands same complex can tune pKa E0, simultaneously. Computational modeling two nickel(II) complexes with 2:1 1:2 ED EW group containing PyS– ligands, respectively, suggests ideal combination is 2:1. also outlines possibility formation large number isomers after protonation one pyridyl N acquire unambiguous results it necessary carefully account for all possible geometric isomers.