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A quadruple helicene with a rubicene core: synthesis, structural analyses and properties

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Abstract

We report the synthesis of a quadruple helicene with a rubicene core R1 by a Scholl reaction. Among the 10 stereoisomers including 4 pairs of enantiomers and 2 meso isomers, only 2 pairs of enantiomers and 1 meso isomer have been isolated. The sample structures were unambiguously determined by X-ray crystallography to be (P,P)6-(P,P)5/(M,M)6-(M,M)5-R1-A, which has a propeller-shaped structure, and (M,M)6-(P,P)5/(P,P)6-(M,M)5-R1-B and (M,P)6-(P,M)5-R1-C, which have saddle-shaped structures. The chiral resolutions of R1 were carried out by chiral HPLC, revealing two pairs of chiral stereoisomers (P,P)6-(P,P)5/(P,P)6-(M,M)5, (M,M)6-(P,P)5/(M,M)6-(M,M)5 as well as a meso isomer (M,P)6-(P,M)5, which were further characterized by CD spectroscopy and time-dependent density functional theory (TD-DFT) calculations. Surprisingly, the UV-vis absorption and emission spectra of these resolved stereoisomers and unresolved R1 were almost identical. In addition, the chemical oxidation of R1 led to the formation of radical cations and dications at room temperature.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (21672026, 21971020).

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Authors and Affiliations

  1. College of Chemistry, Beijing Normal University, Beijing, 100875, China

    Qi Xu, Chu Wang, Dan Zheng, Ying Wang, Xuebo Chen & Hua Jiang

  2. School of Chemistry and Chemical Engineering, Shandong University, Jinan, 250100, China

    Di Sun

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  1. Qi Xu
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  2. Chu Wang
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  3. Dan Zheng
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  4. Ying Wang
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  5. Xuebo Chen
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Correspondence to Hua Jiang.

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Xu, Q., Wang, C., Zheng, D. et al. A quadruple helicene with a rubicene core: synthesis, structural analyses and properties. Sci. China Chem. 64, 590–598 (2021). https://doi.org/10.1007/s11426-020-9913-5

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  • DOI: https://doi.org/10.1007/s11426-020-9913-5

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