We would like to acknowledge Portland State University for funding this project through the Faculty Development Award. The calculations were done on the high-performance computing cluster at Portland State University, which was purchased in part with funds from National Science Foundation (grant DMS 1624776).
ACS Organic & Inorganic Au
Molecular structure -- Water
This work demonstrates a strategy to fine-tune the efficiency of a photoredox water splitting Ni(II) tris-pyridinethiolate catalyst through heteroleptic ligand design using computational investigation of the catalytic mechanism. Density functional theory (DFT) calculations, supported by topology analyses using quantum theory of atoms in molecules (QTAIM), show that the introduction of electron donating (ED) −CH3 and electron withdrawing (EW) −CF3 groups on the thiopyridyl (PyS–) ligands of the same complex can tune the pKa and E0, simultaneously. Computational modeling of two heteroleptic nickel(II) tris-pyridinethiolate complexes with 2:1 and 1:2 ED and EW −CH3 and −CF3 group containing PyS– ligands, respectively, suggests that the ideal combination of EW to ED groups is 2:1. This work also outlines the possibility of formation of a large number of isomers after the protonation of one of the pyridyl N atoms and suggests that to acquire unambiguous computational results it is necessary to carefully account for all possible geometric isomers.
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Bhattacharjee, A., Brown, D. S., Ethridge, T. E., Halvorsen, K. M., Acevedo Montano, A. C., & McCormick, T. M. (2022). Computational Investigation into Heteroleptic Photoredox Catalysts Based on Nickel (II) Tris-Pyridinethiolate for Water Splitting Reactions. ACS Organic & Inorganic Au, 3(1), 41-50.