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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.
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Redox-switchable atom transfer radical polymerization
Temporal control in atom transfer radical polymerization (ATRP) relies on modulating the oxidation state of a copper catalyst, as polymer chains are activated by L/Cu I and deactivated by L/Cu II . (Re)generation of L/Cu I activator has been achieved by applying a multitude of external stimuli. However, switching the Cu catalyst off by oxidizing to L/Cu II through external chemical stimuli has not yet been investigated. A redox switchable ATRP was developed in which an oxidizing agent was used to oxidize L/Cu I activator to L/Cu II , thus halting the polymerization. A ferrocenium salt or oxygen were used to switch off the Cu catalyst, whereas ascorbic acid was used to switch the catalyst on by (re)generating L/Cu I . The redox switches efficiently modulated the oxidation state of the catalyst without sacrificing control over polymerization.
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- Award ID(s):
- 1707490
- PAR ID:
- 10096394
- Date Published:
- Journal Name:
- Chemical Communications
- Volume:
- 55
- Issue:
- 5
- ISSN:
- 1359-7345
- Page Range / eLocation ID:
- 612 to 615
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript
- Journal Article:
- https://doi.org/10.1039/c8cc09209e
