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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| Main Authors: | , , , , |
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| Format: | Article |
| Language: | English |
| Published: |
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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| Summary: | 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. |
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| ISSN: | 2041-1723 |