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

Authors

Avik Bhattacharjee, Portland State UniversityFollow
Dayalis S.V. Brown, Portland State University
Trent E. Ethridge, Portland State University
Kristine M. Halvorsen, Portland State University
Alejandra C. Acevedo Montano, Portland State University
Theresa M. McCormick, Portland State UniversityFollow

Sponsor

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).

Published In

ACS Organic & Inorganic Au

Document Type

Article

Publication Date

10-2022

Subjects

Molecular structure -- Water

Abstract

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 pK_a 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.

Rights

Copyright (c) 2022 The Authors

This work is licensed under a Creative Commons Attribution 4.0 International License.

Locate the Document

https://doi.org/10.1021/acsorginorgau.2c00040

DOI

10.1021/acsorginorgau.2c00040

Persistent Identifier

https://archives.pdx.edu/ds/psu/40999

Citation Details

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.