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

Yang, Chongqing [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry] (ORCID:0000000225388545); Liu, Jianfang [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry] (ORCID:0000000167868873); Khoo, Rebecca Hui [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry] (ORCID:0000000305915894); Abdelsamie, Maged [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry; King Fahd University of Petroleum and Minerals, Dhahran (Saudi Arabia)]; Qi, Miao [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry] (ORCID:0000000322328739); Li, He [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)] (ORCID:0000000240767279); Mao, Haiyan [University of California, Berkeley, CA (United States)]; Hemenway, Sydney [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry] (ORCID:0000000268088235); Xu, Qiang [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)] (ORCID:0000000337474325); Wang, Yunfei [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); University of Southern Mississippi, Hattiesburg, MS (United States)]; Yu, Beihang [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry] (ORCID:0000000150600766); Zhang, Qingsong [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry]; Liu, Xinxin [Beijing Normal University, Beijing (China)]; Klivansky, Liana M. [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry]; Gu, Xiaodan [University of Southern Mississippi, Hattiesburg, MS (United States)] (ORCID:0000000211233673); Zhu, Chenhui [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)]; Reimer, Jeffrey A. [University of California, Berkeley, CA (United States)] (ORCID:0000000241913725); Cui, Ganglong [Beijing Normal University, Beijing (China)] (ORCID:0000000297521659); Sutter-Fella, Carolin M. [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry] (ORCID:0000000277690869); Zhang, Jian [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry] (ORCID:0000000302740814); Ren, Gang [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry] (ORCID:0000000280362321); Liu, Yi [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)] (ORCID:0000000239546102)

doi:10.1038/s41467-025-58822-2

DOE OSTI · 2555864

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

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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.

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Yang, Chongqing [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry] (ORCID:0000000225388545), Liu, Jianfang [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry] (ORCID:0000000167868873), Khoo, Rebecca Hui [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry] (ORCID:0000000305915894), Abdelsamie, Maged [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry; King Fahd University of Petroleum and Minerals, Dhahran (Saudi Arabia)], Qi, Miao [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry] (ORCID:0000000322328739), Li, He [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)] (ORCID:0000000240767279), Mao, Haiyan [University of California, Berkeley, CA (United States)], Hemenway, Sydney [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry] (ORCID:0000000268088235), Xu, Qiang [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)] (ORCID:0000000337474325), Wang, Yunfei [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); University of Southern Mississippi, Hattiesburg, MS (United States)], Yu, Beihang [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry] (ORCID:0000000150600766), Zhang, Qingsong [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry], Liu, Xinxin [Beijing Normal University, Beijing (China)], Klivansky, Liana M. [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry], Gu, Xiaodan [University of Southern Mississippi, Hattiesburg, MS (United States)] (ORCID:0000000211233673), Zhu, Chenhui [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)], Reimer, Jeffrey A. [University of California, Berkeley, CA (United States)] (ORCID:0000000241913725), Cui, Ganglong [Beijing Normal University, Beijing (China)] (ORCID:0000000297521659), Sutter-Fella, Carolin M. [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry] (ORCID:0000000277690869), Zhang, Jian [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry] (ORCID:0000000302740814), Ren, Gang [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry] (ORCID:0000000280362321), Liu, Yi [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)] (ORCID:0000000239546102). 2025-04-12. High-fidelity topochemical polymerization in single crystals, polycrystals, and solution aggregates. https://doi.org/10.1038/s41467-025-58822-2

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