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Unraveling the amplified chiroptical responses of rylene-bladed quintuple [6]helicenes

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Abstract

Unraveling the key structural features to maximize the chiroptical properties is of significance for developing high-performance chiral materials. Here we present our first attempt to elucidate and understand the molecular design of excellent chiroptical properties via the combination of multiplicity and the alignment of subhelicenes. Two stereoisomeric PDI-bladed quintuple [6]helicenes, namely D5-CRP and C2-CRP, were revealed to show distinct spatial arrangements of subhelicenes. Circular dichroism (CD) spectra showed that the Cotton effects (Δε) are reaching 1,412 mol−1 L cm−1 for D5-CRP and 669 mol−1 L cm−1 for C2-CRP in the visible spectrum. The greatly amplified Δε relative to the smaller analogue NPDH arises from the circular annulation of helicenes and high molecular symmetry that could significantly regulate the transition dipole moments and thereby make them tend to be (anti)parallel, as supported by TDDFT calculations for the rotatory strength (R). Consequently, the maximal dissymmetry factors (|gabs| and |glum|) of this kind of chiral molecular carbon imides were estimated to be up to 0.021 and 0.012, respectively. This study provides a deep insight into the chiroptical properties of complicated chiral systems.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (22122503, 22235005, and 22275112), and the Shandong Provincial Natural Science Foundation (ZR2019ZD50). We thank Dr. Dong Meng for his helpful discussions on the crystallo-graphic structural analysis.

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Authors and Affiliations

  1. Key Laboratory of Organic Optoelectronics and Molecular Engineering, Department of Chemistry, Tsinghua University, Beijing, 100084, China

    Yanan Wu, Yujian Liu, Wei Jiang & Zhaohui Wang

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  1. Yanan Wu
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Correspondence to Zhaohui Wang.

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Wu, Y., Liu, Y., Jiang, W. et al. Unraveling the amplified chiroptical responses of rylene-bladed quintuple [6]helicenes. Sci. China Chem. 66, 2400–2407 (2023). https://doi.org/10.1007/s11426-023-1686-4

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  • DOI: https://doi.org/10.1007/s11426-023-1686-4

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