Riboflavin-Catalyzed Photoinduced Atom Transfer Radical Polymerization

Halil Ibrahim Coskun; Thomas Votruba-Drzal; Hanshu Wu; Steffen Jockusch; Gorkem Yilmaz; Krzysztof Matyjaszewski

doi:10.1002/macp.202400323

Riboflavin-Catalyzed Photoinduced Atom Transfer Radical Polymerization

Halil Ibrahim Coskun, Thomas Votruba-Drzal, Hanshu Wu, Steffen Jockusch, Gorkem Yilmaz^*, Krzysztof Matyjaszewski^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

1 Citation (Scopus)

Abstract

The photoATRP of methyl acrylate (MA) is investigated using riboflavin (RF) and CuBr₂/Me₆TREN as a dual catalyst system under green LED irradiation (λ ≈ 525 nm). Both RF and CuBr₂/Me₆TREN enhanced oxygen tolerance, enabling effective ATRP in the presence of residual oxygen. High molar mass polymers (up to M_n ≈ 129 000 g·mol⁻¹) with low dispersity (Đ ≤ 1.16) are prepared, and chain-end fidelity is confirmed through successful chain extension. The molecular masses of the obtained polymer increased linearly with conversion and showed high initiation efficiency. Mechanistic studies by laser flash photolysis reveal that the predominant activator generation mechanism is reductive quenching of RF by Me₆TREN (83%, under [CuBr₂]/[Me₆TREN] = 1/3 condition), supported by polymerization kinetics and thermodynamic calculations.

Original language	English
Article number	2400323
Journal	Macromolecular Chemistry and Physics
Volume	226
Issue number	7
DOIs	https://doi.org/10.1002/macp.202400323
Publication status	Published - Apr 2025
Externally published	Yes

Bibliographical note

Publisher Copyright:
© 2024 The Author(s). Macromolecular Chemistry and Physics published by Wiley-VCH GmbH.

Keywords

ATRP
photocatalyst
photopolymerization
riboflavin

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10.1002/macp.202400323

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@article{229b492a7f7949eea95f21e03afc8723,

title = "Riboflavin-Catalyzed Photoinduced Atom Transfer Radical Polymerization",

abstract = "The photoATRP of methyl acrylate (MA) is investigated using riboflavin (RF) and CuBr2/Me6TREN as a dual catalyst system under green LED irradiation (λ ≈ 525 nm). Both RF and CuBr2/Me6TREN enhanced oxygen tolerance, enabling effective ATRP in the presence of residual oxygen. High molar mass polymers (up to Mn ≈ 129 000 g·mol−1) with low dispersity ({\D} ≤ 1.16) are prepared, and chain-end fidelity is confirmed through successful chain extension. The molecular masses of the obtained polymer increased linearly with conversion and showed high initiation efficiency. Mechanistic studies by laser flash photolysis reveal that the predominant activator generation mechanism is reductive quenching of RF by Me6TREN (83%, under [CuBr2]/[Me6TREN] = 1/3 condition), supported by polymerization kinetics and thermodynamic calculations.",

keywords = "ATRP, photocatalyst, photopolymerization, riboflavin",

author = "Coskun, {Halil Ibrahim} and Thomas Votruba-Drzal and Hanshu Wu and Steffen Jockusch and Gorkem Yilmaz and Krzysztof Matyjaszewski",

note = "Publisher Copyright: {\textcopyright} 2024 The Author(s). Macromolecular Chemistry and Physics published by Wiley-VCH GmbH.",

year = "2025",

month = apr,

doi = "10.1002/macp.202400323",

language = "English",

volume = "226",

journal = "Macromolecular Chemistry and Physics",

issn = "1022-1352",

publisher = "Wiley-VCH Verlag",

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TY - JOUR

T1 - Riboflavin-Catalyzed Photoinduced Atom Transfer Radical Polymerization

AU - Coskun, Halil Ibrahim

AU - Votruba-Drzal, Thomas

AU - Wu, Hanshu

AU - Jockusch, Steffen

AU - Yilmaz, Gorkem

AU - Matyjaszewski, Krzysztof

PY - 2025/4

Y1 - 2025/4

N2 - The photoATRP of methyl acrylate (MA) is investigated using riboflavin (RF) and CuBr2/Me6TREN as a dual catalyst system under green LED irradiation (λ ≈ 525 nm). Both RF and CuBr2/Me6TREN enhanced oxygen tolerance, enabling effective ATRP in the presence of residual oxygen. High molar mass polymers (up to Mn ≈ 129 000 g·mol−1) with low dispersity (Đ ≤ 1.16) are prepared, and chain-end fidelity is confirmed through successful chain extension. The molecular masses of the obtained polymer increased linearly with conversion and showed high initiation efficiency. Mechanistic studies by laser flash photolysis reveal that the predominant activator generation mechanism is reductive quenching of RF by Me6TREN (83%, under [CuBr2]/[Me6TREN] = 1/3 condition), supported by polymerization kinetics and thermodynamic calculations.

AB - The photoATRP of methyl acrylate (MA) is investigated using riboflavin (RF) and CuBr2/Me6TREN as a dual catalyst system under green LED irradiation (λ ≈ 525 nm). Both RF and CuBr2/Me6TREN enhanced oxygen tolerance, enabling effective ATRP in the presence of residual oxygen. High molar mass polymers (up to Mn ≈ 129 000 g·mol−1) with low dispersity (Đ ≤ 1.16) are prepared, and chain-end fidelity is confirmed through successful chain extension. The molecular masses of the obtained polymer increased linearly with conversion and showed high initiation efficiency. Mechanistic studies by laser flash photolysis reveal that the predominant activator generation mechanism is reductive quenching of RF by Me6TREN (83%, under [CuBr2]/[Me6TREN] = 1/3 condition), supported by polymerization kinetics and thermodynamic calculations.

KW - ATRP

KW - photocatalyst

KW - photopolymerization

KW - riboflavin

UR - http://www.scopus.com/inward/record.url?scp=105001829151&partnerID=8YFLogxK

U2 - 10.1002/macp.202400323

DO - 10.1002/macp.202400323

M3 - Article

AN - SCOPUS:105001829151

SN - 1022-1352

VL - 226

JO - Macromolecular Chemistry and Physics

JF - Macromolecular Chemistry and Physics

IS - 7

M1 - 2400323

ER -

Riboflavin-Catalyzed Photoinduced Atom Transfer Radical Polymerization

Abstract

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Keywords

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