Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 17, Issue 52, Pages 15027-15031Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201101445
Keywords
iridium; photochemistry; photoredox catalysis; ring-opening polymerization; silyl radicals
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Funding
- Agence Nationale de la Recherche [ANR 2010-BLAN-0802]
- Institut Universitaire de France IUF
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Iridium(III) complexes were designed and evaluated as efficient photoinitiators of polymerization reactions in combination with iodonium salts and silanes. Mechanistically, these reactions were shown to proceed through oxidative photoredox catalysis, generating aryl and silyl radicals under very soft irradiation conditions (blue LED, xenon lamp, and even sunlight). These radicals can initiate the free radical polymerization of acrylates or can be oxidized during the catalytic cycle to promote the ring-opening polymerization of epoxy monomers. Remarkably, both the (photo)chemical reactivity and the practical efficiency are dramatically affected by the ligands. In addition, the central role played by the oxidation ability of the excited state of the photocatalyst is discussed.
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