Abstract
Multi-axis atropisomers are ubiquitous in nature, and their intricate stereoconformations not only deepen stereochemical understanding but also elucidate fundamental principles of molecular atropisomeric dynamics. Nevertheless, insights into multi-axis atropisomerism remain limited. This work presents a systematic investigation of three classes of LaPlente-type biaxial atropisomers based on naphthalene rotors and phenyl linkers. Thermodynamically and kinetically controlled interconversion of molecular conformations is achieved in 22-NB, 11-NB, and 11-NB-8DMe. Concurrently, a direct correlation between molecular dynamics and electronic through-space conjugation (TSC) is elucidated. Furthermore, absolute separation of syn and anti conformers is accomplished in 11-NB-2DMe, whose distinct TSC-induced fluorescence enables direct visualization of dynamic conformer populations and kinetics during temporally sequential crystallization. This work provides fundamental mechanistic insights into multi-axis atropisomer stereochemistry and establishes a fluorescence-based approach as an in-situ platform for real-time analysis of molecular dynamics across life and materials sciences.
Data availability
The crystallographic data for the structures reported in this article have been deposited at the Cambridge Crystallographic Data Centre (CCDC) under deposition numbers 2470573 (22-NB), 2470574 (11-NB), 2470575 (111-NB), 2470576 (11-NB-8DMe), 2470577 (11-NB-2DMe-syn), 2470578 (11-NB-2DMe-anti). These data can be obtained free of charge from CCDC via www.ccdc.cam.ac.uk/data_request/cif. All the data supporting the findings in this work are available within the manuscript and Supplementary Information file and available from the corresponding authors upon request.
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Acknowledgements
This work is supported by the National Natural Science Foundation of China (No. 224B2509, received by Q.X.; No. 22575211, received by H.Z.; No. 524B2036, received by Z.X.; No. 52503253, received by J.Z.), the Fundamental Research Funds for the Central Universities (No. 226-2025-00031, received by H.Z.; No. 226-2025-00091, received by J.Z.), the Open Fund of the State Key Laboratory of Luminescent Materials and Devices (South China University of Technology, received by H.Z.), Seed Program of China Petroleum & Chemical Corporation (Sinopec, received by H.Z.), the Large Instruments Open Foundation of Nantong University (KFJN2551, received by Y.W.). We thank Yingying Zhang from the Testing and Analysis Center of the Department of Polymer Science and Engineering at Zhejiang University for the assistance in performing Photoluminescence Spectroscopy measurements. We thank Jiyong Liu from the Testing and Analysis Center of the Department of Chemistry at Zhejiang University for the help in performing X-ray single crystal diffractometer measurements. We thank the Guangdong Provincial Key Laboratory of Luminescence from Molecular Aggregates for the help in quantum mechanical calculations.
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Q.X., J.Z., and H.Z. conceived and designed the experiments. Q.X., and K.L. performed the synthesis and the photophysical measurements. Q.X. conducted theoretical calculations. J.W., H.L., M.C., and Z.X. provided significant assistance with the experimental measurements. Q.X., J.Z., and H.Z. analyzed the data. Q.X., Y.W., J.Z.S, J.Z., F.H., B.Z.T., and H.Z. took part in the discussion and gave important suggestions. Q.X., J.Z., and H.Z. co-wrote the paper.
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Xu, Q., Luo, K., Wang, Y. et al. Fluorescence mapping of atropisomer populations enabled by through-space conjugation. Nat Commun (2026). https://doi.org/10.1038/s41467-026-69109-5
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DOI: https://doi.org/10.1038/s41467-026-69109-5
