Issue 13, 2021

β-Diketiminate-supported iridium photosensitizers with increased excited-state reducing power

Abstract

A series of bis-cyclometalated iridium complexes were prepared which combine triazole or NHC-based cyclometalating ligands with substituted β-diketiminate (NacNac) ancillary ligands. The HOMO is localized on the NacNac ligand and its energy and associated redox potential are determined by the NacNac substitution pattern. The effect of the cyclometalating ligand, relative to the more common 2-phenylpyridine derivatives, is to destabilize the LUMO and increase the triplet excited-state energy (ET1). These results are supported by DFT calculations, which show HOMOs and LUMOs that are respectively localized on the NacNac and cyclometalating ligands. With this new design, we observe more negative excited-state reduction potentials, E(IrIV/*IrIII), with two members of the series standing out as the most potent visible-light iridium photoreductants ever reported. Stern–Volmer quenching experiments with ketone acceptors (benzophenone and acetophenone) show that the increased thermodynamic driving force for photoinduced electron-transfer correlates with faster rates relative to fac-Ir(ppy)3 and previous generations of NacNac-supported iridium complexes. A small selection of photoredox transformations is shown, demonstrating that these new photoreductants are capable of activating challenging organohalide substrates, albeit with modest conversion.

Graphical abstract: β-Diketiminate-supported iridium photosensitizers with increased excited-state reducing power

Supplementary files

Article information

Article type
Research Article
Submitted
22 Mar 2021
Accepted
14 May 2021
First published
17 May 2021

Inorg. Chem. Front., 2021,8, 3253-3265

Author version available

β-Diketiminate-supported iridium photosensitizers with increased excited-state reducing power

J. Shon, D. Kim, T. G. Gray and T. S. Teets, Inorg. Chem. Front., 2021, 8, 3253 DOI: 10.1039/D1QI00382H

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