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Selective Photoactivation of Trithiocarbonates Mediated by Metal Naphthalocyanines and Overcoming Activation Barriers Using Thermal Energy

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    Selective Photoactivation of Trithiocarbonates Mediated by Metal Naphthalocyanines and Overcoming Activation Barriers Using Thermal Energy
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    • Zilong Wu
      Zilong Wu
      College of Materials Science and Engineering, Institute for Graphene Applied Technology Innovation, Collaborative Innovation Centre for Marine Biomass Fibers, Materials and Textiles of Shandong Province, Qingdao University, Qingdao 266071, China
      Cluster for Advanced Macromolecular Design and Australian Centre for NanoMedicine, School of Chemical Engineering, The University of New South Wales, Sydney, New South Wales 2052, Australia
      More by Zilong Wu
    • Kenward Jung
      Kenward Jung
      Cluster for Advanced Macromolecular Design and Australian Centre for NanoMedicine, School of Chemical Engineering, The University of New South Wales, Sydney, New South Wales 2052, Australia
      More by Kenward Jung
    • Chenyu Wu
      Chenyu Wu
      Qingdao Institute for Theoretical and Computational Sciences, Shandong University, Qingdao 266237, China
      More by Chenyu Wu
    • Gervase Ng
      Gervase Ng
      Cluster for Advanced Macromolecular Design and Australian Centre for NanoMedicine, School of Chemical Engineering, The University of New South Wales, Sydney, New South Wales 2052, Australia
      More by Gervase Ng
    • Lei Wang
      Lei Wang
      College of Materials Science and Engineering, Institute for Graphene Applied Technology Innovation, Collaborative Innovation Centre for Marine Biomass Fibers, Materials and Textiles of Shandong Province, Qingdao University, Qingdao 266071, China
      More by Lei Wang
    • Jingquan Liu*
      Jingquan Liu
      College of Materials Science and Engineering, Institute for Graphene Applied Technology Innovation, Collaborative Innovation Centre for Marine Biomass Fibers, Materials and Textiles of Shandong Province, Qingdao University, Qingdao 266071, China
      *Email: [email protected]
      More by Jingquan Liu
      Orcidhttps://orcid.org/0000-0001-6178-8661
    • Cyrille Boyer*
      Cyrille Boyer
      Cluster for Advanced Macromolecular Design and Australian Centre for NanoMedicine, School of Chemical Engineering, The University of New South Wales, Sydney, New South Wales 2052, Australia
      *Email: [email protected]
      More by Cyrille Boyer
      Orcidhttps://orcid.org/0000-0002-4564-4702
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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2022, 144, 2, 995–1005
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    https://doi.org/10.1021/jacs.1c11700
    Published January 10, 2022
    Copyright © 2022 American Chemical Society
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    Abstract

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    Metal naphthalocyanines (MNcs) were demonstrated to be efficient photocatalysts to activate photoinduced electron-transfer reversible addition–fragmentation chain transfer (PET-RAFT) polymerization, enabling well-controlled polymerization of (meth)acrylates under near-infrared (λ = 780 nm) light. Owing to their lower redox potential compared to previously explored photocatalysts, the activation of trithiocarbonate RAFT agents exhibited a unique selectivity that was dependent on the nature of the R group. Specifically, MNcs were capable in activating tertiary R group trithiocarbonates, whereas no activation of the trithiocarbonate possessing a secondary R group was observed. The combination of density functional theory calculations and experimental studies have revealed new mechanistic insights into the factors governing a PET-RAFT mechanism and explained this unique selectivity of MNcs toward tertiary carbon trithiocarbonates. Interestingly, by increasing the reaction temperature moderately (i.e., ∼15 °C), the energy barrier prohibiting the photoactivation of the trithiocarbonate with a secondary R group was overcome, enabling their successful activation.

    Copyright © 2022 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.1c11700.

    • Experimental section, DFT calculation, additional references, Schemes S1 and S2, Figures S1–S28, and Tables S1–S11 (PDF)

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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2022, 144, 2, 995–1005
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jacs.1c11700
    Published January 10, 2022
    Copyright © 2022 American Chemical Society
    Request reuse permissions

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