期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 138, 期 35, 页码 11399-11407出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.6b08068
关键词
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资金
- University of Colorado Boulder
- Advanced Research Projects Agency-Energy [DE-AR0000683]
- American Chemical Society Petroleum Research Fund [56501-DNI7]
- National Institute of General Medical Sciences of the National Institutes of Health [R35GM119702]
- University of Colorado Department of Chemistry and Biochemistry Marian Sharrah Fellowship
- NSF [CHE-1214131]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1214131] Funding Source: National Science Foundation
N-Aryl phenoxazines have been synthesized and introduced as strongly reducing metal-free photoredox catalysts in organocatalyzed atom transfer radical polymerization for the synthesis of well-defined polymers. Experiments confirmed quantum chemical predictions that, like their dihydrophenazine analogs, the photoexcited states of phenoxazine photoredox catalysts are strongly reducing and achieve superior performance when they possess charge transfer character. We compare phenoxazines to previously reported dihydrophenazines and phenothiazines as photoredox catalysts to gain insight into the performance of these catalysts and establish principles for catalyst design. A key finding reveals that maintenance of a planar conformation of the phenoxazine catalyst during the catalytic cycle encourages the synthesis of well-defined macromolecules. Using these principles, we realized a core substituted phenoxazine as a visible light photoredox catalyst that performed superior to UV-absorbing phenoxazines as well as previously reported organic photocatalysts in organocatalyzed atom transfer radical polymerization. Using this catalyst and irradiating with white LEDs resulted in the production of polymers with targeted molecular weights through achieving quantitative initiator efficiencies, which possess dispersities ranging from 1.13 to 1.31.
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