Enlightening the mechanism of copper mediated photoRDRP via high-resolution mass spectrometry

Frick, Elena, Anastasaki, Athina, Haddleton, David M., & Barner-Kowollik, Christopher (2015) Enlightening the mechanism of copper mediated photoRDRP via high-resolution mass spectrometry. Journal of the American Chemical Society, 137(21), pp. 6889-6896.

View at publisher


The initiation mechanism of photochemically mediated Cu-based reversible-deactivation radical polymerization (photoRDRP) was investigated using pulsed-laser polymerization (PLP) and high-resolution mass spectrometry. The variation of the catalyst composition and ESI-MS analysis of the resulting products provided information on how initiator, ligand, copper species, and monomer are interacting upon irradiation with UV light. A discussion of the results allows for a new postulation of the mechanism of photoRDRP and–for the first time–the unambiguous identification of the initiating species and their interactions within the reaction mixture. One pathway for radical generation proceeds via UV light-induced C–Br bond scission of the initiator, giving rise to propagating radicals. The generation of copper(I) species from copper(II) can occur via several pathways, including, among others, via reduction by free amine ligand in its excited as well as from its ground state via the irradiation with UV light. The amine ligand serves as a strong reducing agent and is likely the main participant in the generation of copper(I) species.

Impact and interest:

40 citations in Scopus
Search Google Scholar™
39 citations in Web of Science®

Citation counts are sourced monthly from Scopus and Web of Science® citation databases.

These databases contain citations from different subsets of available publications and different time periods and thus the citation count from each is usually different. Some works are not in either database and no count is displayed. Scopus includes citations from articles published in 1996 onwards, and Web of Science® generally from 1980 onwards.

Citations counts from the Google Scholar™ indexing service can be viewed at the linked Google Scholar™ search.

ID Code: 97039
Item Type: Journal Article
Refereed: Yes
DOI: 10.1021/jacs.5b03048
ISSN: 1520-5126
Divisions: Current > Schools > School of Chemistry, Physics & Mechanical Engineering
Current > Institutes > Institute for Future Environments
Current > QUT Faculties and Divisions > Science & Engineering Faculty
Copyright Owner: Copyright 2015 American Chemical Society
Deposited On: 11 Aug 2016 23:23
Last Modified: 15 Aug 2016 01:47

Export: EndNote | Dublin Core | BibTeX

Repository Staff Only: item control page