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Construction of chiral through-space luminophores via symmetry breaking triggered by sequenced chlorination

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Abstract

The construction of molecular chirality is crucial for exploring novel luminophores with chiroptical properties. Classic asymmetric synthesis of chiral center or axial is not powerful enough on through-space architecture. Accessible methodologies for breaking molecular symmetry could be promising but remain less investigated. Herein, we report a novel methodology for constructing chiral through-space luminophores via simple chlorination on bridged carbazole motifs. The chlorination breaks the molecular symmetry and thus results in molecular chirality by eliminating the mirror plane or rotating axis. Interestingly, continuous multiple chlorinations can rebuild and break the symmetry of the skeleton in succession. Several chiral and achiral isomeric analogues are synthesized and characterized with impressive chiroptical properties. Results of chiral high performance liquid chromatography (HPLC), single-crystal X-ray diffraction, kinetic racemization, and chiroptical property investigation demonstrate the effectiveness of our rational design strategy. It provides a feasible methodology for exploring novel chiral luminescent materials based on versatile though-space skeletons.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (21975061) and Shenzhen Fundamental Research Program (JCYJ20190806142403535, GXWD2020123015542700 320200728150952003).

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Author notes

  1. These authors contributed equally to this work.

Authors and Affiliations

  1. School of Science, Harbin Institute of Technology, Shenzhen, 518055, China

    Yufeng Xie, Huaying Liu, Lijuan Song, Feng Yuan, Hengzhi You, Engui Zhao & Zikai He

  2. School of Chemical Engineering and Technology, Harbin Institute of Technology Harbin, Harbin, 150001, China

    Yufeng Xie, Hengzhi You & Zikai He

  3. Academy for Advanced Interdisciplinary Studies and Department of Chemistry, Southern University of Science and Technology, Shenzhen, 518055, China

    Zhongliang Li

  4. Shenzhen Bay Laboratory, Shenzhen, 518055, China

    Xin Zhang

  5. Hoffmann Institute of Advanced Materials, Shenzhen Polytechnic, Shenzhen, 518055, China

    Kang Zhou

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  1. Yufeng Xie
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  2. Huaying Liu
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  3. Zhongliang Li
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  4. Xin Zhang
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  5. Lijuan Song
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  6. Kang Zhou
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  7. Feng Yuan
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  8. Hengzhi You
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  9. Engui Zhao
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  10. Zikai He
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Correspondence to Zikai He.

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The supporting information is available online at http://chem.scichina.com and http://link.springer.com/journal/. The supporting materials are published as submitted, without typesetting or editing. The responsibility for scientific accuracy and content remains entirely with the authors.

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Xie, Y., Liu, H., Li, Z. et al. Construction of chiral through-space luminophores via symmetry breaking triggered by sequenced chlorination. Sci. China Chem. 66, 2083–2090 (2023). https://doi.org/10.1007/s11426-023-1560-0

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  • DOI: https://doi.org/10.1007/s11426-023-1560-0

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