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High-fidelity topochemical polymerization in single crystals, polycrystals, and solution aggregates

Author

Listed:
  • Chongqing Yang

    (Lawrence Berkeley National Laboratory)

  • Jianfang Liu

    (Lawrence Berkeley National Laboratory)

  • Rebecca Shu Hui Khoo

    (Lawrence Berkeley National Laboratory)

  • Maged Abdelsamie

    (Lawrence Berkeley National Laboratory
    King Fahd University of Petroleum and Minerals (KFUPM))

  • Miao Qi

    (Lawrence Berkeley National Laboratory)

  • He Li

    (Lawrence Berkeley National Laboratory
    Lawrence Berkeley National Laboratory)

  • Haiyan Mao

    (University of California)

  • Sydney Hemenway

    (Lawrence Berkeley National Laboratory)

  • Qiang Xu

    (Lawrence Berkeley National Laboratory)

  • Yunfei Wang

    (Lawrence Berkeley National Laboratory
    Lawrence Berkeley National Laboratory
    The University of Southern Mississippi)

  • Beihang Yu

    (Lawrence Berkeley National Laboratory)

  • Qingsong Zhang

    (Lawrence Berkeley National Laboratory)

  • Xinxin Liu

    (Beijing Normal University)

  • Liana M. Klivansky

    (Lawrence Berkeley National Laboratory)

  • Xiaodan Gu

    (The University of Southern Mississippi)

  • Chenhui Zhu

    (Lawrence Berkeley National Laboratory)

  • Jeffrey A. Reimer

    (University of California)

  • Ganglong Cui

    (Beijing Normal University)

  • Carolin M. Sutter-Fella

    (Lawrence Berkeley National Laboratory)

  • Jian Zhang

    (Lawrence Berkeley National Laboratory)

  • Gang Ren

    (Lawrence Berkeley National Laboratory)

  • Yi Liu

    (Lawrence Berkeley National Laboratory
    Lawrence Berkeley National Laboratory)

Abstract

Topochemical polymerization (TCP) emerges as a leading approach for synthesizing single crystalline polymers, but is traditionally restricted to transformations in solid-medium. The complexity in achieving single-crystal-to-single-crystal (SCSC) transformations due to lattice disparities and the untapped potential of performing TCP in a liquid medium with solid-state structural fidelity present unsolved challenges. Herein, by using X-rays as the primary means to overcome crystal disintegration, we reveal the details of SCSC transformation during the TCP of chiral azaquinodimethane (AQM) monomers through in situ crystallographic analysis while spotlighting a rare metastable crystalline phase. Complementary in situ investigations of powders and thin films provide critical insights into the side-chain dependent polymerization kinetics of solid-state reactions. Furthermore, we enable TCP of AQM monomers in a liquid medium via an antisolvent-reinforced aggregated state, yielding polymer nanofibers with high crystallinity akin to that of solid-state. This study testifies high structural precision of TCP performed in different states and media, offering critical insights into the synthesis of processable nanostructured polymers with desired structural integrity.

Suggested Citation

  • Chongqing Yang & Jianfang Liu & Rebecca Shu Hui Khoo & Maged Abdelsamie & Miao Qi & He Li & Haiyan Mao & Sydney Hemenway & Qiang Xu & Yunfei Wang & Beihang Yu & Qingsong Zhang & Xinxin Liu & Liana M. , 2025. "High-fidelity topochemical polymerization in single crystals, polycrystals, and solution aggregates," Nature Communications, Nature, vol. 16(1), pages 1-10, December.
    • Handle: RePEc:nat:natcom:v:16:y:2025:i:1:d:10.1038_s41467-025-58822-2
    DOI: 10.1038/s41467-025-58822-2
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