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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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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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.
The authors declare no competing interests.
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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