Work

Red-Light-Induced Ligand-to-Metal Charge Transfer Catalysis by Tuning the Axial Coordination of Cobyrinate

Year: 2024

Type: article

Abstract: Photoinduced ligand-to-metal charge transfer (LMCT) is a powerful technique for the formation of reactive radical species via homolytic cleavage of the metal-ligand bond. Here, we present that the excited state LMCT of a cobyrinate complex can be accessed by tuning its axial coordination with thiolates as ligands. We demonstrate the photoreduction of cobalt via the excited state Co-S bond homolytic cleavage, as guided by the DFT calculations, which signify the relevance of thiolate axial ligands facilitating the LMCT reactivity. By exploiting this excited state LMCT of cobyrinate, we developed a catalyst-controlled activator regeneration mechanism to catalyze an efficient atom transfer radical polymerization (ATRP) under low-energy light irradiation. Tuning the coordination sphere of cobyrinate provides further control over the electronic properties of the complex while also accessing photothermal conversion in mediating ATRP catalysis.

Source: Journal of the American Chemical Society

DOI: 10.1021/jacs.4c12432

Authors: Sajjad Dadashi-Silab, Cristina Preston-Herrera, Daniel G. Oblinsky, Gregory D. Scholes, Erin E. Stache

Institution: Princeton University

Language: English

Topic: Radical Photochemical Reactions

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: green