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    Soluble and Processable Single-Crystalline Cationic Polymers
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    • Yang Liu
      Yang Liu
      Stoddart Institute of Molecular Science, Department of Chemistry, Zhejiang University, Hangzhou 310027, China
      ZJU-Hangzhou Global Scientific and Technological Innovation Center, Hangzhou 311215, China
      More by Yang Liu
    • Xin-Ru Guan
      Xin-Ru Guan
      Stoddart Institute of Molecular Science, Department of Chemistry, Zhejiang University, Hangzhou 310027, China
      ZJU-Hangzhou Global Scientific and Technological Innovation Center, Hangzhou 311215, China
      More by Xin-Ru Guan
    • Duan-Chao Wang
      Duan-Chao Wang
      Stoddart Institute of Molecular Science, Department of Chemistry, Zhejiang University, Hangzhou 310027, China
      ZJU-Hangzhou Global Scientific and Technological Innovation Center, Hangzhou 311215, China
      More by Duan-Chao Wang
      Orcidhttps://orcid.org/0000-0002-3133-4041
    • J. Fraser Stoddart*
      J. Fraser Stoddart
      Stoddart Institute of Molecular Science, Department of Chemistry, Zhejiang University, Hangzhou 310027, China
      ZJU-Hangzhou Global Scientific and Technological Innovation Center, Hangzhou 311215, China
      Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United States
      School of Chemistry, University of New South Wales, Sydney, NSW 2052, Australia
      *Email: [email protected]
      More by J. Fraser Stoddart
      Orcidhttps://orcid.org/0000-0003-3161-3697
    • Qing-Hui Guo*
      Qing-Hui Guo
      Stoddart Institute of Molecular Science, Department of Chemistry, Zhejiang University, Hangzhou 310027, China
      ZJU-Hangzhou Global Scientific and Technological Innovation Center, Hangzhou 311215, China
      *Email: [email protected]
      More by Qing-Hui Guo
      Orcidhttps://orcid.org/0000-0002-9946-0810
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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2023, 145, 24, 13223–13231
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jacs.3c02266
    Published June 9, 2023
    Copyright © 2023 American Chemical Society
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    Abstract

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    Single-crystal-to-single-crystal (SCSC) polymerization offers an effective protocol for the environmentally friendly preparation of polymer single crystals (PSCs) with extremely high crystallinity and very large molecular weights. Single-crystal X-ray diffraction (SCXRD) serves as a powerful technique for the in-depth characterization of their structures at a molecular level. Hence, a fundamental understanding of the structure–property relationships of PSCs is within our reach. Most of the reported PSCs, however, suffer from poor solubility, a property which hampers their post-functionalization and solution processability when it comes to practical applications. Here, we report soluble and processable PSCs with rigid polycationic backbones by taking advantage of an ultraviolet-induced topochemical polymerization from an elaborately designed monomer that results in a multitude of photoinduced [2 + 2] cycloadditions. The high crystallinity and excellent solubility of the resulting polymeric crystals enable their characterization both in the solid state by X-ray crystallography and electron microscopy and in the solution phase by NMR spectroscopy. The topochemical polymerization follows first-order reaction kinetics to a first approximation. Post-functionalization of the PSCs by anion exchange renders them super-hydrophobic materials for water purification. Solution processability endows PSCs with excellent gel-like rheological properties. This research represents a major step towards the controlled synthesis and full characterization of soluble single-crystalline polymers, which may find application in the fabrication of PSCs with many different functions.

    Copyright © 2023 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.3c02266.

    • Detailed information regarding the experimental methods and procedures, X-ray crystallographic data, and supporting figures and tables (PDF)

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    CCDC 2223226–2223227 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2023, 145, 24, 13223–13231
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jacs.3c02266
    Published June 9, 2023
    Copyright © 2023 American Chemical Society
    Request reuse permissions

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