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      Open-air green-light-driven ATRP enabled by dual photoredox/copper catalysis†

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          Abstract

          Photoinduced atom transfer radical polymerization (photo-ATRP) has risen to the forefront of modern polymer chemistry as a powerful tool giving access to well-defined materials with complex architecture. However, most photo-ATRP systems can only generate radicals under biocidal UV light and are oxygen-sensitive, hindering their practical use in the synthesis of polymer biohybrids. Herein, inspired by the photoinduced electron transfer-reversible addition–fragmentation chain transfer (PET-RAFT) polymerization, we demonstrate a dual photoredox/copper catalysis that allows open-air ATRP under green light irradiation. Eosin Y was used as an organic photoredox catalyst (PC) in combination with a copper complex (X–Cu II/L). The role of PC was to trigger and drive the polymerization, while X–Cu II/L acted as a deactivator, providing a well-controlled polymerization. The excited PC was oxidatively quenched by X–Cu II/L, generating Cu I/L activator and PC˙ +. The ATRP ligand (L) used in excess then reduced the PC˙ +, closing the photocatalytic cycle. The continuous reduction of X–Cu II/L back to Cu I/L by excited PC provided high oxygen tolerance. As a result, a well-controlled and rapid ATRP could proceed even in an open vessel despite continuous oxygen diffusion. This method allowed the synthesis of polymers with narrow molecular weight distributions and controlled molecular weights using Cu catalyst and PC at ppm levels in both aqueous and organic media. A detailed comparison of photo-ATRP with PET-RAFT polymerization revealed the superiority of dual photoredox/copper catalysis under biologically relevant conditions. The kinetic studies and fluorescence measurements indicated that in the absence of the X–Cu II/L complex, green light irradiation caused faster photobleaching of eosin Y, leading to inhibition of PET-RAFT polymerization. Importantly, PET-RAFT polymerizations showed significantly higher dispersity values (1.14 ≤ Đ ≤ 4.01) in contrast to photo-ATRP (1.15 ≤ Đ ≤ 1.22) under identical conditions.

          Abstract

          Fully oxygen-tolerant photoinduced atom transfer radical polymerization (photo-ATRP) allowed the synthesis of well-defined polymers using a Cu catalyst and eosin Y at ppm levels in both aqueous and organic media.

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          Author and article information

          Journal
          Chem Sci
          Chem Sci
          SC
          CSHCBM
          Chemical Science
          The Royal Society of Chemistry
          2041-6520
          2041-6539
          20 September 2022
          12 October 2022
          20 September 2022
          : 13
          : 39
          : 11540-11550
          Affiliations
          [a] Department of Chemistry, Carnegie Mellon University Pittsburgh Pennsylvania 15213 USA gszczepa@ 123456andrew.cmu.edu matyjaszewski@ 123456cmu.edu
          [b] Faculty of Chemistry, University of Warsaw Pasteura 1 02-093 Warsaw Poland
          [c] Department of Biomedical Engineering, Carnegie Mellon University Pittsburgh Pennsylvania 15213 USA
          [d] Faculty of Chemistry, Adam Mickiewicz University, Uniwersytetu Poznańskiego 8 61-614 Poznań Poland
          [e] Center for Nucleic Acids Science & Technology, Carnegie Mellon University Pittsburgh Pennsylvania 15213 USA
          Author notes
          [‡]

          J.J. and K.K. contributed equally to this work.

          Author information
          https://orcid.org/0000-0002-0355-9542
          https://orcid.org/0000-0002-1453-0964
          https://orcid.org/0000-0002-4285-5846
          https://orcid.org/0000-0002-3437-2852
          https://orcid.org/0000-0003-0179-6023
          https://orcid.org/0000-0002-5353-0422
          https://orcid.org/0000-0003-1960-3402
          Article
          d2sc04210j
          10.1039/d2sc04210j
          9557244
          36320395
          0e908a80-6df9-42ea-b538-b2d71f5ce59a
          This journal is © The Royal Society of Chemistry
          History
          : 28 July 2022
          : 19 September 2022
          Page count
          Pages: 11
          Funding
          Funded by: Kosciuszko Foundation, doi 10.13039/100001724;
          Award ID: Unassigned
          Funded by: National Science Foundation, doi 10.13039/100000001;
          Award ID: CHE-2000391
          Funded by: Ministerstwo Edukacji i Nauki, doi 10.13039/501100004569;
          Award ID: 1646/MOB/V/2017/0
          Categories
          Chemistry
          Custom metadata
          Paginated Article

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