IDEAS home Printed from https://ideas.repec.org/a/nat/natcom/v16y2025i1d10.1038_s41467-025-59222-2.html
   My bibliography  Save this article

Halogen bond-modulated solid-state reordering and symmetry breaking of azahelicenes

Author

Listed:
  • Juncong Liang

    (Shanghai Jiao Tong University)

  • Fuwei Gan

    (Shanghai Jiao Tong University)

  • Guoli Zhang

    (Shanghai Jiao Tong University)

  • Chengshuo Shen

    (Zhejiang Sci-Tech University)

  • Huibin Qiu

    (Shanghai Jiao Tong University)

Abstract

Spontaneous symmetry breaking predominately occurs during the aggregation of discrete molecules in solution. Herein, we report a unique solid-state symmetry breaking process of dynamically chiral aza[4]helicenes that emerged in vacuum-driven transformation of halogen bond-woven crystals. Due to the weak feature of the halogen bonding, the halides in the cocrystals can be completely removed under vacuum at an elevated temperature. Interestingly, the aza[4]helicene molecules released from the halogen bond network solely adopt one chiral conformation upon reordering and symmetry breaking instantly occurs in a solid state. The Cotton effects gradually increase with the extension of vacuum–heating treatment, indicating a unidirectional transformation of the chiral conformations and an amplification of symmetry breaking during the solid-state reorganization. Moreover, the use of aza[6]helicene as a chiral inducer further enables a precise manipulation for the absolute configuration of the solid-state symmetry breaking, paving a distinctive route to chiral organic materials from achiral/racemic precursors.

Suggested Citation

  • Juncong Liang & Fuwei Gan & Guoli Zhang & Chengshuo Shen & Huibin Qiu, 2025. "Halogen bond-modulated solid-state reordering and symmetry breaking of azahelicenes," Nature Communications, Nature, vol. 16(1), pages 1-10, December.
    • Handle: RePEc:nat:natcom:v:16:y:2025:i:1:d:10.1038_s41467-025-59222-2
    DOI: 10.1038/s41467-025-59222-2
    as

    Download full text from publisher

    File URL: https://www.nature.com/articles/s41467-025-59222-2
    File Function: Abstract
    Download Restriction: no
    File URL: https://libkey.io/10.1038/s41467-025-59222-2?utm_source=ideas
    LibKey link: if access is restricted and if your library uses this service, LibKey will redirect you to where you can use your library subscription to access this item
    ---><---

    References listed on IDEAS

    as
    1. Shinnosuke Horiuchi & Takumi Yamaguchi & Jacopo Tessarolo & Hirotaka Tanaka & Eri Sakuda & Yasuhiro Arikawa & Eric Meggers & Guido H. Clever & Keisuke Umakoshi, 2023. "Symmetry-breaking host–guest assembly in a hydrogen-bonded supramolecular system," Nature Communications, Nature, vol. 14(1), pages 1-9, December.
    2. Zhaocun Shen & Yutao Sang & Tianyu Wang & Jian Jiang & Yan Meng & Yuqian Jiang & Kou Okuro & Takuzo Aida & Minghua Liu, 2019. "Asymmetric catalysis mediated by a mirror symmetry-broken helical nanoribbon," Nature Communications, Nature, vol. 10(1), pages 1-8, December.
    3. Chengshuo Shen & Guoli Zhang & Yongle Ding & Na Yang & Fuwei Gan & Jeanne Crassous & Huibin Qiu, 2021. "Oxidative cyclo-rearrangement of helicenes into chiral nanographenes," Nature Communications, Nature, vol. 12(1), pages 1-8, December.
    Full references (including those not matched with items on IDEAS)

    Most related items

    These are the items that most often cite the same works as this one and are cited by the same works as this one.
    1. Guoli Zhang & Jian Zhang & Yu Tao & Fuwei Gan & Geyu Lin & Juncong Liang & Chengshuo Shen & Yuebiao Zhang & Huibin Qiu, 2024. "Facile fabrication of recyclable robust noncovalent porous crystals from low-symmetry helicene derivative," Nature Communications, Nature, vol. 15(1), pages 1-8, December.
    2. Ran Chen & Ahmad Hammoud & Paméla Aoun & Mayte A. Martínez-Aguirre & Nicolas Vanthuyne & Régina Maruchenko & Patrick Brocorens & Laurent Bouteiller & Matthieu Raynal, 2024. "Switchable supramolecular helices for asymmetric stereodivergent catalysis," Nature Communications, Nature, vol. 15(1), pages 1-11, December.
    3. Chengwen Li & Ying-Bo Shao & Xi Gao & Zhiyuan Ren & Chenhao Guo & Meng Li & Xin Li, 2023. "Enantioselective synthesis of chiral quinohelicenes through sequential organocatalyzed Povarov reaction and oxidative aromatization," Nature Communications, Nature, vol. 14(1), pages 1-9, December.
    4. Calum J. Gibb & Jordan Hobbs & Diana I. Nikolova & Thomas Raistrick & Stuart R. Berrow & Alenka Mertelj & Natan Osterman & Nerea Sebastián & Helen F. Gleeson & Richard. J. Mandle, 2024. "Spontaneous symmetry breaking in polar fluids," Nature Communications, Nature, vol. 15(1), pages 1-9, December.

    More about this item

    Statistics

    Access and download statistics

    Corrections

    All material on this site has been provided by the respective publishers and authors. You can help correct errors and omissions. When requesting a correction, please mention this item's handle: RePEc:nat:natcom:v:16:y:2025:i:1:d:10.1038_s41467-025-59222-2. See general information about how to correct material in RePEc.

    If you have authored this item and are not yet registered with RePEc, we encourage you to do it here. This allows to link your profile to this item. It also allows you to accept potential citations to this item that we are uncertain about.

    If CitEc recognized a bibliographic reference but did not link an item in RePEc to it, you can help with this form .

    If you know of missing items citing this one, you can help us creating those links by adding the relevant references in the same way as above, for each refering item. If you are a registered author of this item, you may also want to check the "citations" tab in your RePEc Author Service profile, as there may be some citations waiting for confirmation.

    For technical questions regarding this item, or to correct its authors, title, abstract, bibliographic or download information, contact: Sonal Shukla or Springer Nature Abstracting and Indexing (email available below). General contact details of provider: http://www.nature.com .

    Please note that corrections may take a couple of weeks to filter through the various RePEc services.

    IDEAS is a RePEc service. RePEc uses bibliographic data supplied by the respective publishers.