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Chemistry. 2011 Dec 23;17(52):15027-31. doi: 10.1002/chem.201101445. Epub 2011 Nov 28.

Subtle ligand effects in oxidative photocatalysis with iridium complexes: application to photopolymerization.

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  • 1Institut de Science des Matériaux de Mulhouse, IS2M, LRC CNRS 7228-ENSCMu-UHA, 15, rue Jean Starcky, 68057 Mulhouse Cedex, France.


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.

Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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