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Low-symmetry coordination cages enable recognition specificity and selective enrichment of higher fullerene isomers

Nature Synthesis volume 4, pages 359–369 (2025)Cite this article

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Abstract

The discovery of buckminsterfullerene (C60) marked a milestone in exploring three-dimensional carbon materials. However, with the exponential increase in the number of isomers for higher fullerenes, it has become challenging to realize the enrichment of the isomers by molecular recognition. Here we report two pseudo-cubic metal–organic cages, T and S4, with distinct cavity microenvironments, that showcase recognition specificity towards higher fullerene isomers. Compared with cage T, a symmetry shift from S4 to C2 emerges upon encapsulating an ellipsoidal D2-C76 guest, owing to the precise shape matching that curtails guest rotation. Furthermore, the low-symmetry cage S4 shows exceptional sensitivity in distinguishing between closely related isomers, such as a pair of C2v-symmetric C78 isomers, and shows promise for the selective enrichment of higher fullerenes. The approach of reducing symmetry positions metal–organic cages as promising candidates for encapsulating and identifying a broader spectrum of fullerene isomers, paralleling the specificity observed in biological systems.

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Fig. 1: Host–guest recognition of various fullerene isomers by supramolecular hosts.
Fig. 2: Synthesis and characterization of high-symmetry assemblies.
Fig. 3: Synthesis and characterization of low-symmetry assemblies.
Fig. 4: Solid-state structures of assemblies.
Fig. 5: Comparison of recognition sensitivity of T- and S4-symmetric cages.
Fig. 6: Recognition of C2v-symmetric C78 isomers with T- and S4-symmetric cages.

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Data availability

Crystallographic data are available free of charge from the Cambridge Crystallographic Data Centre under reference CCDC no. 2278920 (C2v-C78), 2278921 (C2v′-C78), 2307962 (C3-1), 2307963 (P-1), 2307964(4), 2307965 (T-3), 2307966 (C60⊂S4-4) and 2307967 (C70⊂S4-4). These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via https://www.ccdc.cam.ac.uk/structures/. All other data supporting the findings of this study are available in the Article or the Supplementary Information.

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Acknowledgements

This work was supported by the National Key Research and Development Program of China (grants 2022YFA1503300 and 2021YFA1500400 to Q.-F.S. and grant 2022YFB3807700 to X.L.), National Natural Science Foundation of China (grant 22201285 to X.-Q.G., grant 22171264 to Q.-F.S., grants 21925104 and 92261204 to X.L. and grant 61825107 to Q.-F.S.) and Science Foundation of Fujian Province (grant 202lJ02016 to Q.-F.S.). We thank the staff of BL17B1 beamline at National Centre for Protein Sciences Shanghai and Shanghai Synchrotron Radiation Facility (SSRF), Shanghai, People’s Republic of China, for assistance during data collection.

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Author notes

  1. These authors contributed equally: Xiao-Qing Guo, Pengwei Yu.

Authors and Affiliations

  1. State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, People’s Republic of China

    Xiao-Qing Guo, Li-Peng Zhou, Shao-Jun Hu, Xiao-Fang Duan, Li-Xuan Cai & Qing-Fu Sun

  2. State Key Laboratory of Materials Processing and Die and Mould Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, Wuhan, People’s Republic of China

    Pengwei Yu, Lipiao Bao & Xing Lu

  3. University of Chinese Academy of Sciences, Beijing, People’s Republic of China

    Xiao-Fang Duan & Qing-Fu Sun

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Contributions

Q.-F.S., X.L., X.-Q.G., P.Y. and L.B. conceived the project, carried out research, analysed all experiments and wrote the manuscript. L.-P.Z. performed the mass measurements. L.-X.C. and S.-J.H. contributed to X-ray crystallographic analysis. X.-F.D. contributed to the figure production. All authors discussed the results and commented on the manuscript.

Corresponding authors

Correspondence to Xing Lu or Qing-Fu Sun.

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The authors declare no competing interests.

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Peer review information

Nature Synthesis thanks Jonathan Charmant, Xavi Ribas, Giuseppe Trusso Sfrazzetto 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

Supplementary Figs. 1–162 and Tables 1–27.

Supplementary Data 1

Crystallographic data for C2v-C78 (CCDC reference 2278920).

Supplementary Data 2

Crystallographic data for C2v′-C78 (CCDC reference 2278921).

Supplementary Data 3

Crystallographic data for C3-1 (CCDC reference 2307962).

Supplementary Data 4

Crystallographic data for P-1 (CCDC reference 2307963).

Supplementary Data 5

Crystallographic data for 4 (CCDC reference 2307964).

Supplementary Data 6

Crystallographic data for T-3 (CCDC reference 2307965).

Supplementary Data 7

Crystallographic data for C60⊂S4-4 (CCDC reference 2307966).

Supplementary Data 8

Crystallographic data for C70⊂S4-4 (CCDC reference 2307967).

Source data

Source Data Fig. 2

ESI-TOF-MS of T-3.

Source Data Fig. 3

ESI-TOF-MS of S4-4 and C60⊂S4-4.

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Guo, XQ., Yu, P., Zhou, LP. et al. Low-symmetry coordination cages enable recognition specificity and selective enrichment of higher fullerene isomers. Nat. Synth 4, 359–369 (2025). https://doi.org/10.1038/s44160-024-00697-0

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