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Highly efficient organic photocatalysts discovered via a computer-aided-design strategy for visible-light-driven atom transfer radical polymerization

Nature Catalysis volume 1, pages 794–804 (2018)Cite this article

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Abstract

Organocatalysed photoredox-mediated atom transfer radical polymerization (O-ATRP) is a very promising polymerization method as it eliminates concerns associated with transition-metal contamination of polymer products. However, reducing the amount of catalyst and expanding the monomer scope remain major challenges in O-ATRP. Herein, we report a systematic computer-aided-design strategy to identify powerful visible-light photoredox catalysts for O-ATRP. One of our discovered organic photoredox catalysts controls the polymerization of methyl methacrylate at sub-ppm catalyst loadings (0.5 ppm—a very meaningful amount enabling the direct use of polymers without a catalyst removal process); that is, 100–1,000 times lower loadings than other organic photoredox catalysts reported so far. Another organic photoredox catalyst with supra-reducing power in an excited state and high redox stability facilitates the challenging polymerization of the non-acrylic monomer styrene, which is not successful using existing photoredox catalysts. This work provides access to diverse challenging organic/polymer syntheses and makes O-ATRP viable for many industrial and biomedical applications.

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Fig. 1: Strategy for OPC design.
Fig. 2: Molecular structures of OPCs.
Fig. 3: Analyses of the photophysical and electrochemical properties of OPCs.
Fig. 4: Photophysical and electrochemical properties of 2c.
Fig. 5: Photophysical and electrochemical properties of 4g.

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The data that support the findings of this study are available within the article and its Supplementary Information, and from the corresponding author upon reasonable request.

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Acknowledgements

This work was supported by the 2018 Research Fund (1.180067.01) of the Ulsan National Institute of Science and Technology, and Basic Science Research Program through the National Research Foundation of Korea (NRF), which was funded by the Ministry of Education (NRF–2016R1D1A1B03936002) and National Honor Scientist Program (2010–0020414) of the NRF. The work at IMDEA was supported by the ‘Severo Ochoa’ programme for Centers of Excellence in Research and Development (MINECO; grant SEV–2016–0686), European Union structural funds and Comunidad de Madrid MAD2D-CM Program (S2013/MIT–3007), and Campus of International Excellence UAM + CSIC. Financial support at IMDEA and the University of Valencia was further provided by the Spanish Ministry for Science (MINECO–FEDER projects CTQ2014–58801 and CTQ2017–87054).

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Authors and Affiliations

  1. Department of Materials Science and Engineering, Ulsan National Institute of Science and Technology, Ulsan, Republic of Korea

    Varun Kumar Singh, Changhoon Yu, Sachin Badgujar, Youngmu Kim, Yonghwan Kwon, Doyon Kim, Junhyeok Lee, Toheed Akhter, Gurunathan Thangavel, Lee Soon Park & Min Sang Kwon

  2. Department of Chemistry, Ulsan National Institute of Science and Technology, Ulsan, Republic of Korea

    Toheed Akhter & Kwang S. Kim

  3. Department Chemical Engineering, Ulsan National Institute of Science and Technology, Ulsan, Republic of Korea

    Jiseok Lee

  4. Madrid Institute for Advanced Studies, IMDEA Nanociencia, Madrid, Spain

    Paramjyothi C. Nandajan, Reinhold Wannemacher, Begoña Milián-Medina, Larry Lüer & Johannes Gierschner

  5. Department for Physical Chemistry, Faculty of Chemistry, University of Valencia, Valencia, Spain

    Begoña Milián-Medina

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Contributions

M.S.K. conceived and supervised the project. K.S.K. and J.G. supported and assisted in supervising the project. V.K.S. and M.S.K. designed the experiments and analysed the data. V.K.S. and C.Y. performed most of the experiments. S.B., Y.Kim, Y.Kwon, D.K., J.L., T.A. and G.T. helped with the synthesis of OPCs and polymerization studies. P.C.N., R.W. and L.L. performed advanced photophysical measurements. B.M.-M. and J.G. carried out the quantum chemical calculations. L.S.P. and J.L. advised on the experiments. V.K.S., K.S.K., J.G. and M.S.K. prepared the manuscript, with contributions from all authors.

Corresponding authors

Correspondence to Kwang S. Kim, Johannes Gierschner or Min Sang Kwon.

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Supplementary Methods, Supplementary Notes 1–7, Supplementary Figures 1–86, Supplementary Tables 1–10 and Supplementary References

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Singh, V.K., Yu, C., Badgujar, S. et al. Highly efficient organic photocatalysts discovered via a computer-aided-design strategy for visible-light-driven atom transfer radical polymerization. Nat Catal 1, 794–804 (2018). https://doi.org/10.1038/s41929-018-0156-8

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