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Synthesis and chiral resolution of a triply twisted Möbius carbon nanobelt

Nature Synthesis volume 2, pages 880–887 (2023)Cite this article

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Abstract

The atomically precise synthesis of topological molecular carbons such as Möbius carbon nanobelts (MCNBs) is a challenge in synthetic organic chemistry because it requires careful control of both twist and strain. So far, only one singly twisted MCNB has been reported and MCNBs with more than two twists remain unknown. Herein we report the facile synthesis of a triply twisted MCNB by rational design via a synthetic route involving Suzuki coupling-mediated macrocyclization, Bi(OTf)3-catalysed cyclization of vinyl ethers and oxidative dehydrogenation. The Möbius band-like structure was confirmed by X-ray crystallographic analysis, which also revealed the coexistence of (P,P,P) and (M,M,M) enantiomers. The racemic isomers were resolved by chiral HPLC and the isolated enantiomers exhibited a large absorption dissymmetry factor (|gabs| = 0.019) according to circular dichroism spectroscopy, which can be explained by the fully conjugated structure and the desirable orientation of the electric and magnetic transition moments.

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Fig. 1: Möbius strip-like molecules with an odd number of twists.
Fig. 2: Synthetic route to the triply twisted Möbius carbon nanobelt 1.
Fig. 3: X-ray crystallographic structures of 2a and 1.
Fig. 4: Calculated StrainViz maps for 2a/2b and 1.
Fig. 5: Calculated 3D ICSS maps and LOL-π isosurface.
Fig. 6: Photophysical and chiroptical properties.

Data availability

Crystallographic data for the structures reported in this article have been deposited at the Cambridge Crystallographic Data Centre, under deposition numbers CCDC 2242047 (2a) and 2242048 (1). Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/. The experimental data and the characterization data are available in the Supplementary Information.

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Acknowledgements

J.W. acknowledges financial support through an A*STAR AME IRG grant (A20E5c0089) and an NRF Investigatorship award (NRF-NRFI05-2019-0005). H.I. and T.M.F. thank KAKENHI (20H05672 and 22K20527) for financial support.

Author information

Author notes

  1. These authors contributed equally: Wei Fan, Toshiya M. Fukunaga.

Authors and Affiliations

  1. Department of Chemistry, National University of Singapore, Singapore, Singapore

    Wei Fan, Shaofei Wu, Yi Han, Qifeng Zhou, Jinyi Wang, Zhengtao Li, Xudong Hou, Haipeng Wei, Yong Ni & Jishan Wu

  2. Department of Chemistry, The University of Tokyo, Tokyo, Japan

    Toshiya M. Fukunaga & Hiroyuki Isobe

  3. Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Fuzhou, China

    Qifeng Zhou & Jishan Wu

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Contributions

J.Wu and W.F. conceived the concept, designed the project and prepared the manuscript. H.I. and T.M.F. performed the chiral HPLC experiments, CD and CPL measurements and data analysis, and prepared the manuscript. W.F. performed the synthesis. W.F., J.Wang and X.H. performed the photophysical measurements. S.W., Y.H., H.W. and Y.N. contributed to the X-ray crystallographic analyses. W.F., Y.H., Q.Z. and Z.L. performed the computational studies.

Corresponding authors

Correspondence to Hiroyuki Isobe or Jishan Wu.

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The authors declare no competing interests.

Peer review

Peer review information

Nature Synthesis thanks Juan Casado Cordon and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary Handling Editor: Alison Stoddart, in collaboration with the Nature Synthesis team.

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Supplementary information

Supplementary Information

Experimental Section, Figs. 1–35, Tables 1–5, and NMR and mass spectra.

Supplementary Data 1

Cartesian coordinates of optimized structures from DFT calculations.

Supplementary Data 2

Crystal data for 2a (CCDC 2242047).

Supplementary Data 3

Crystal data for 1 (CCDC 2242048).

Source data

Source Data Fig. 6

Raw data of the absorption, fluorescence and CD spectra of 2b and 1.

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Fan, W., Fukunaga, T.M., Wu, S. et al. Synthesis and chiral resolution of a triply twisted Möbius carbon nanobelt. Nat. Synth 2, 880–887 (2023). https://doi.org/10.1038/s44160-023-00317-3

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