Halogen bond-modulated solid-state reordering and symmetry breaking of azahelicenes
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. Du...
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2025-04-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-025-59222-2 |
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| author | Juncong Liang Fuwei Gan Guoli Zhang Chengshuo Shen Huibin Qiu |
| author_facet | Juncong Liang Fuwei Gan Guoli Zhang Chengshuo Shen Huibin Qiu |
| author_sort | Juncong Liang |
| collection | DOAJ |
| description | 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. |
| format | Article |
| id | doaj-art-a3c3ae13fb434702b910143a5baefd3d |
| institution | OA Journals |
| issn | 2041-1723 |
| language | English |
| publishDate | 2025-04-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-a3c3ae13fb434702b910143a5baefd3d2025-08-20T02:30:26ZengNature PortfolioNature Communications2041-17232025-04-0116111010.1038/s41467-025-59222-2Halogen bond-modulated solid-state reordering and symmetry breaking of azahelicenesJuncong Liang0Fuwei Gan1Guoli Zhang2Chengshuo Shen3Huibin Qiu4School of Chemistry and Chemical Engineering, State Key Laboratory of Synergistic Chem-Bio Synthesis, Frontiers Science Center for Transformative Molecules, Zhangjiang Institute for Advanced Study, State Key Laboratory of Micro-Nano Engineering Science, Shanghai Jiao Tong UniversitySchool of Chemistry and Chemical Engineering, State Key Laboratory of Synergistic Chem-Bio Synthesis, Frontiers Science Center for Transformative Molecules, Zhangjiang Institute for Advanced Study, State Key Laboratory of Micro-Nano Engineering Science, Shanghai Jiao Tong UniversitySchool of Chemistry and Chemical Engineering, State Key Laboratory of Synergistic Chem-Bio Synthesis, Frontiers Science Center for Transformative Molecules, Zhangjiang Institute for Advanced Study, State Key Laboratory of Micro-Nano Engineering Science, Shanghai Jiao Tong UniversitySchool of Chemistry and Chemical Engineering, Zhejiang Sci-Tech UniversitySchool of Chemistry and Chemical Engineering, State Key Laboratory of Synergistic Chem-Bio Synthesis, Frontiers Science Center for Transformative Molecules, Zhangjiang Institute for Advanced Study, State Key Laboratory of Micro-Nano Engineering Science, Shanghai Jiao Tong UniversityAbstract 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.https://doi.org/10.1038/s41467-025-59222-2 |
| spellingShingle | Juncong Liang Fuwei Gan Guoli Zhang Chengshuo Shen Huibin Qiu Halogen bond-modulated solid-state reordering and symmetry breaking of azahelicenes Nature Communications |
| title | Halogen bond-modulated solid-state reordering and symmetry breaking of azahelicenes |
| title_full | Halogen bond-modulated solid-state reordering and symmetry breaking of azahelicenes |
| title_fullStr | Halogen bond-modulated solid-state reordering and symmetry breaking of azahelicenes |
| title_full_unstemmed | Halogen bond-modulated solid-state reordering and symmetry breaking of azahelicenes |
| title_short | Halogen bond-modulated solid-state reordering and symmetry breaking of azahelicenes |
| title_sort | halogen bond modulated solid state reordering and symmetry breaking of azahelicenes |
| url | https://doi.org/10.1038/s41467-025-59222-2 |
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