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Mesolytic Versus Homolytic Cleavage in Photochemical Nitroxide-Mediated Polymerization

Hill, Nicholas; Fule, Melinda; Morris, Jason; Clement, Jean-Louis; Guillaneuf, Yohann; Gigmes, Didier; Coote, Michelle

Description

Time-dependent density functional theory calculations have been performed to study the photocleavage reactions of chromophore-functionalized alkoxyamines in nitroxide-mediated photopolymerization. Two case studies were considered: azaphenalene derivatives and benzophenone-based alkoxyamines. For the azaphenalenes, we show that the expected homolysis pathway is actually inaccessible. Instead, these alkoxyamines exhibit low-lying nNπ* excited states that exhibit an electronic structure about...[Show more]

CollectionsANU Research Publications
Date published: 2020
Type: Journal article
URI: http://hdl.handle.net/1885/268543
Source: Macromolecules
DOI: 10.1021/acs.macromol.0c00134
Access Rights: Open Access

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