Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 57, Issue 26, Pages 7898-7902Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201802964
Keywords
block copolymers; controlled radical polymerization; copper; NIR sensitizers; photocatalysis
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Funding
- BMBF (FHProfUnt) [03FH022PX4]
- county of North Rhine-Westphalia [005-1703-0006]
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NIR-sensitized photoinduced atom-transfer radical polymerization (ATRP) is possible by using ppm of Cu-II/tris(2-pyridylmethyl)amine (TPMA) as the catalyst, a polymethine as the photosensitizer, and alpha-bromophenylacetate as the alkyl halide initiator. Among the polymethines investigated with cationic, zwitterionic, or anionic structures, only the zwitterionic 2 exhibited sensitization activity under NIR light at room temperature resulting in the formation of polymers with controlled molecular weight characteristics and functionalities. The barbital group placed at the mesa-position of 2 caused the activity in this photo-ATRP framework. The chain-end fidelity of the polymers was confirmed by chain extension and block copolymerization experiments. The polymerization system exhibits high photostability under NIR light exposure and irradiation dependency as demonstrated by light on/off experiments.
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