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

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 Klivansky; Xiaodan Gu; Chenhui Zhu; Jeffrey A Reimer; Ganglong Cui; Carolin M Sutter-Fella; Jian Zhang; Gang Ren; Yi Liu

doi:10.1038/s41467-025-58822-2

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

Nat Commun. 2025 Apr 12;16(1):3498. doi: 10.1038/s41467-025-58822-2.

Authors

Chongqing Yang^#¹, Jianfang Liu^#¹, Rebecca Shu Hui Khoo¹, Maged Abdelsamie^{1

2}, Miao Qi¹, He Li^{1

3}, Haiyan Mao⁴, Sydney Hemenway¹, Qiang Xu⁵, Yunfei Wang^{1

6

7}, Beihang Yu¹, Qingsong Zhang¹, Xinxin Liu⁸, Liana M Klivansky¹, Xiaodan Gu⁷, Chenhui Zhu⁶, Jeffrey A Reimer⁴, Ganglong Cui⁸, Carolin M Sutter-Fella¹, Jian Zhang¹, Gang Ren¹, Yi Liu^{9

10}

Affiliations

¹ The Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, CA, 94720, USA.
² Interdisciplinary Research Center for Intelligent Manufacturing and Robotics, King Fahd University of Petroleum and Minerals (KFUPM), Dhahran, 31261, Saudi Arabia.
³ Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, 94720, USA.
⁴ Department of Chemical and Biomolecular Engineering, University of California, Berkeley, CA, 94720, USA.
⁵ Chemical Science Division, Lawrence Berkeley National Laboratory, Berkeley, CA, 94720, USA.
⁶ Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA, 94720, USA.
⁷ School of Polymer Science and Engineering Center for Optoelectronic Materials and Devices, The University of Southern Mississippi, Hattiesburg, MS, 39406, USA.
⁸ Key Laboratory of Theoretical and Computational Photochemistry, Ministry of Education, Chemistry College, Beijing Normal University, Beijing, 100875, P.R. China.
⁹ The Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, CA, 94720, USA. yliu@lbl.gov.
¹⁰ Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, 94720, USA. yliu@lbl.gov.

^# Contributed equally.

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.

Abstract

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