Near-Infrared Sensitized Photoinduced Atom-Transfer Radical Polymerization (ATRP) with a Copper(II) Catalyst Concentration in the ppm Range

Ceren Kütahya; Christian Schmitz; Veronika Strehmel; Yusuf Yagci; Bernd Strehmel

doi:10.1002/anie.201802964

Near-Infrared Sensitized Photoinduced Atom-Transfer Radical Polymerization (ATRP) with a Copper(II) Catalyst Concentration in the ppm Range

Angew Chem Int Ed Engl. 2018 Jun 25;57(26):7898-7902. doi: 10.1002/anie.201802964. Epub 2018 May 16.

Authors

Ceren Kütahya¹, Christian Schmitz¹, Veronika Strehmel², Yusuf Yagci³, Bernd Strehmel¹

Affiliations

¹ Department of Chemistry and Institute for Coatings and Surface Chemistry, Niederrhein University of Applied Sciences, Adlerstrasse 1, 47798, Krefeld, Germany.
² Department of Chemistry and Institute for Coatings and Surface Chemistry, Niederrhein University of Applied Sciences, Adlerstrasse 32, 47798, Krefeld, Germany.
³ Department of Chemistry, Faculty of Science and Letters, Istanbul Technical University, 34469, Maslak, Istanbul, Turkey.

PMID: 29637671
DOI: 10.1002/anie.201802964

Abstract

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 α-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 meso-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.

Keywords: NIR sensitizers; block copolymers; controlled radical polymerization; copper; photocatalysis.

Publication types

Research Support, Non-U.S. Gov't