Effects of the Chalcogenide Identity in N -Aryl Phenochalcogenazine Photoredox Catalysts.

Autor: Corbin DA; Department of Chemistry Colorado State University 200 W. Lake St. Fort Collins Colorado 80523 United States., Cremer C; Institute of Organic Chemistry RWTH Aachen University Landoltweg 1 52074 Aachen Germany., Puffer KO; Department of Chemistry Colorado State University 200 W. Lake St. Fort Collins Colorado 80523 United States., Newell BS; Analytical Resources Core, Materials and Molecular Analysis Center Colorado State University 200 W. Lake St. Fort Collins Colorado 80523 United States., Patureau FW; Institute of Organic Chemistry RWTH Aachen University Landoltweg 1 52074 Aachen Germany., Miyake GM; Department of Chemistry Colorado State University 200 W. Lake St. Fort Collins Colorado 80523 United States.
Jazyk: angličtina
Zdroj: ChemCatChem [ChemCatChem] 2022 Sep 07; Vol. 14 (17), pp. e202200485. Date of Electronic Publication: 2022 Jul 08.
DOI: 10.1002/cctc.202200485
Abstrakt: Phenochalcogenazines such as phenoxazines and phenothiazines have been widely employed as photoredox catalysts (PCs) in small molecule and polymer synthesis. However, the effect of the chalcogenide in these catalysts has not been fully investigated. In this work, a series of four phenochalcogenazines is synthesized to understand how the chalcogenide impacts catalyst properties and performance. Increasing the size of the chalcogenide is found to distort the PC structure, ultimately impacting the properties of each PC. For example, larger chalcogenides destabilize the PC radical cation, possibly resulting in catalyst degradation. In addition, PCs with larger chalcogenides experience increased reorganization during electron transfer, leading to slower electron transfer. Ultimately, catalyst performance is evaluated in organocatalyzed atom transfer radical polymerization and a photooxidation reaction for C(sp 2 )-N coupling. Results from these experiments highlight that a balance of PC properties is most beneficial for catalysis, including a long-lived excited state, a stable radical cation, and a low reorganization energy.
Competing Interests: The authors declare no conflict of interest.
(© 2022 The Authors. ChemCatChem published by Wiley-VCH GmbH.)
Databáze: MEDLINE
Externí odkaz:
Nepřihlášeným uživatelům se plný text nezobrazuje