High-fidelity topochemical polymerization in single crystals, polycrystals, and solution aggregates
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.
Authors
- Ganglong Cui (ORCID: https://orcid.org/0000-0002-9752-1659)
- Haiyan Mao (ORCID: https://orcid.org/0000-0003-0591-1236)
- Rebecca Shu Hui Khoo
- Chenhui Zhu (ORCID: https://orcid.org/0000-0002-7452-2288)
- Chongqing Yang (ORCID: https://orcid.org/0000-0002-2538-8545)
- Maged Abdelsamie
- Gang Ren (ORCID: https://orcid.org/0000-0002-8036-2321)
- Qiang Xu (ORCID: https://orcid.org/0000-0003-3747-4325)
- Liana M. Klivansky
- Jeffrey A. Reimer (ORCID: https://orcid.org/0000-0002-4191-3725)
- Carolin M. Sutter‐Fella (ORCID: https://orcid.org/0000-0002-7769-0869)
- Jian Zhang (ORCID: https://orcid.org/0000-0003-0274-0814)
- Xiaodan Gu (ORCID: https://orcid.org/0000-0002-1123-3673)
- Beihang Yu (ORCID: https://orcid.org/0000-0001-5060-0766)
- Sydney Hemenway
- He Li (ORCID: https://orcid.org/0000-0002-4076-7279)
- Yi Liu (ORCID: https://orcid.org/0000-0002-3954-6102)
- Xinxin Liu (ORCID: https://orcid.org/0000-0003-0627-5585)
- Yunfei Wang (ORCID: https://orcid.org/0000-0001-7555-5308)
- Miao Qi (ORCID: https://orcid.org/0000-0003-2232-8739)
- Qingsong Zhang (ORCID: https://orcid.org/0000-0001-7893-2447)
- Jianfang Liu (ORCID: https://orcid.org/0000-0001-6786-8873)
Institutions
- King Fahd University of Petroleum and Minerals (SA)
- Lawrence Berkeley National Laboratory (US)
- Beijing Normal University (CN)
- University of Southern Mississippi (US)
- University of California, Berkeley (US)
Publication Details
- Journal
- Nature Communications
- Published
- 2025-04-12
- DOI
- https://doi.org/10.1038/s41467-025-58822-2
- Citations
- 2
- Primary Topic
- Polydiacetylene-based materials and applications
- Type
- article
- Field-Weighted Citation Impact
- 1.87
Funders
- U.S. Department of Energy
- National Institutes of Health
- Office of Science
- Basic Energy Sciences
- Laboratory Directed Research and Development