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Photoredox RAFT polymerisation

Photo-induced Electron/energy Transfer-Reversible Additon-Fragmentation Chain Transfer (PET-RAFT) polymerisation, activated by photoredox catalysts, is a recently developed versatile photocontrolled polymerisation technique capable of polymerising a broad range of both conjugated monomers (acrylates, methacrylates, acrylamides, methacrylamides and styrene) and unconjugated monomers (vinyl esters, N-vinyl pyrrolidinone and dimethyl vinylphosphonate).


Our overarching goal in this area is to develop a robust and versatile toolbox for visible light polymerisation mediated by RAFT to overcome limitations posed by thermal polymerisation.

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A recent focus in this field is the investigation of structure-property-performance in photoredox catalysis of PET-RAFT.

Related publications

  • Wu, C.;  Jung, K.;  Ma, Y.;  Liu, W.; Boyer, C., Unravelling an oxygen-mediated reductive quenching pathway for photopolymerisation under long wavelengths. Nature Communications 2021, 12 (1), 478. Read More​

  • Wu, C.; Chen, H.; Corrigan, N.; Jung, K.; Kan, X.; Li, Z.; Liu, W.; Xu, J.; Boyer, C., Computer-Guided Discovery of a pH-Responsive Organic Photocatalyst and Application for pH and Light Dual-Gated Polymerization. Journal of the American Chemical Society 2019, 10.1021/jacs.9b01096. Read More​

  • Wu, C., Corrigan, N., Lim, C.H., Jung, K., Zhu, J., Miyake, G., Xu, J. and Boyer, C., 2018. Guiding the Design of Organic Photocatalyst for PET-RAFT Polymerization: Halogenated Xanthene Dyes. Macromolecules 2018, 52 (1), 236-248. Read More​

  • Yeow, J.; Joshi, S.; Chapman, R.; Boyer, C., A Self‐Reporting Photocatalyst for Online Fluorescence Monitoring of High Throughput RAFT Polymerization. Angewandte Chemie International Edition 2018, 57 (32), 10102-10106.

  • Wu, C.; Shanmugam, S.; Xu, J.; Zhu, J.; Boyer, C., Chlorophyll a crude extract: Efficient photo-degradable photocatalyst for PET-RAFT polymerization. Chemical Communications 2017, 53 (93), 12560-12563, 10.1039/c7cc07663k.​

  • Xu, J.; Fu, C.; Shanmugam, S.; Hawker, C. J.; Moad, G.; Boyer, C., Synthesis of Discrete Oligomers by Sequential PET-RAFT Single-Unit Monomer Insertion. Angewandte Chemie International Edition 2017, 56 (29), 8376-8383.

  • Xu, J.; Shanmugam, S.; Fu, C.; Aguey-Zinsou, K. F.; Boyer, C., Selective Photoactivation: From a Single Unit Monomer Insertion Reaction to Controlled Polymer Architectures. Journal of the American Chemical Society 2016, 138 (9), 3094-106.

  • Shanmugam, S.; Xu, J.; Boyer, C., Light-Regulated Polymerization under Near-Infrared/Far-Red Irradiation Catalyzed by Bacteriochlorophyll a. Angewandte Chemie International Edition 2016, 55 (3), 1036-40.

  • Shanmugam, S.; Boyer, C., Stereo-, Temporal and Chemical Control through Photoactivation of Living Radical Polymerization: Synthesis of Block and Gradient Copolymers. Journal of the American Chemical Society 2015, 137 (31), 9988-99.

  • Shanmugam, S.; Xu, J.; Boyer, C., Exploiting Metalloporphyrins for Selective Living Radical Polymerization Tunable over Visible Wavelengths. Journal of the American Chemical Society 2015, 137 (28), 9174-85.

  • Xu, J. T.; Shanmugam, S.; Duong, H. T.; Boyer, C., Organo-photocatalysts for photoinduced electron transfer-reversible addition-fragmentation chain transfer (PET-RAFT) polymerization. Polymer Chemistry 2015, 6 (31), 5615-5624.

  • Xu, J. T.; Shanmugam, S.; Boyer, C., Organic Electron Donor-Acceptor Photoredox Catalysts: Enhanced Catalytic Efficiency toward Controlled Radical Polymerization. ACS Macro Letters 2015, 4 (9), 926-932.

  • Shanmugam, S.; Xu, J. T.; Boyer, C., Utilizing the electron transfer mechanism of chlorophyll a under light for controlled radical polymerization. Chemical Science 2015, 6 (2), 1341-1349.

  • Xu, J.; Jung, K.; Atme, A.; Shanmugam, S.; Boyer, C., A robust and versatile photoinduced living polymerization of conjugated and unconjugated monomers and its oxygen tolerance. Journal of the American Chemical Society 2014, 136 (14), 5508-19.

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