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Hierarchical single-crystal-to-single-crystal transformations of a monomer to a 1D-polymer and then to a 2D-polymer

Author

Listed:
  • Haripriya Balan

    (Indian Institute of Science Education and Research Thiruvananthapuram)

  • Kana M. Sureshan

    (Indian Institute of Science Education and Research Thiruvananthapuram)

Abstract

Designing and synthesizing flawless two-dimensional polymers (2D-Ps) via meticulous molecular preorganization presents an intriguing yet challenging frontier in research. We report here the single-crystal-to-single-crystal (SCSC) synthesis of a 2D-P via thermally induced topochemical azide-alkyne cycloaddition (TAAC) reaction. A designed monomer incorporating two azide and two alkyne units is synthesized. The azide and alkyne groups are preorganized in the monomer crystal in reactive geometries for polymerizations in two orthogonal directions. On heating, the polymerizations proceed in a hierarchical manner; at first, the monomer reacts regiospecifically in a SCSC fashion to form a 1,5-triazolyl-linked 1D polymer (1D-P), which upon further heating undergoes another SCSC polymerization to a 2D-P through a second regiospecific TAAC reaction forming 1,4-triazolyl-linkages. Two different linkages in orthogonal directions make this an architecturally attractive 2D-P, as determined, at atomic resolution, by single-crystal X-ray diffraction. The 2D-P reported here is thermally stable in view of the robust triazole-linkages and can be exfoliated as 2D-sheets.

Suggested Citation

  • Haripriya Balan & Kana M. Sureshan, 2024. "Hierarchical single-crystal-to-single-crystal transformations of a monomer to a 1D-polymer and then to a 2D-polymer," Nature Communications, Nature, vol. 15(1), pages 1-10, December.
    • Handle: RePEc:nat:natcom:v:15:y:2024:i:1:d:10.1038_s41467-024-51051-z
    DOI: 10.1038/s41467-024-51051-z
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    References listed on IDEAS

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    1. Feng Shao & Wei Wang & Weimin Yang & Zhilin Yang & Yao Zhang & Jinggang Lan & A. Dieter Schlüter & Renato Zenobi, 2021. "In-situ nanospectroscopic imaging of plasmon-induced two-dimensional [4+4]-cycloaddition polymerization on Au(111)," Nature Communications, Nature, vol. 12(1), pages 1-10, December.
    2. Zhengbang Wang & Alfred Błaszczyk & Olaf Fuhr & Stefan Heissler & Christof Wöll & Marcel Mayor, 2017. "Molecular weaving via surface-templated epitaxy of crystalline coordination networks," Nature Communications, Nature, vol. 8(1), pages 1-8, April.
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