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A three-shell supramolecular complex enables the symmetry-mismatched chemo- and regioselective bis-functionalization of C60

Nature Chemistry volume 13, pages 420–427 (2021)Cite this article

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Abstract

Molecular Russian dolls (matryoshkas) have proven useful for testing the limits of preparative supramolecular chemistry but applications of these architectures to problems in other fields are elusive. Here we report a three-shell, matryoshka-like complex—in which C60 sits inside a cycloparaphenylene nanohoop, which in turn is encapsulated inside a self-assembled nanocapsule—that can be used to address a long-standing challenge in fullerene chemistry, namely the selective formation of a particular fullerene bis-adduct. Spectroscopic evidence indicates that the ternary complex is sufficiently stable in solution for the two outer shells to affect the addition chemistry of the fullerene guest. When the complex is subjected to Bingel cyclopropanation conditions, the exclusive formation of a single trans-3 fullerene bis-adduct was observed in a reaction that typically yields more than a dozen products. The selectivity facilitated by this matryoshka-like approach appears to be a general phenomenon and could be useful for applications where regioisomerically pure C60 bis-adducts have been shown to have superior properties compared with isomer mixtures.

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Fig. 1: Strategies reported for the regioselective synthesis of C60 adducts.
Fig. 2: Synthesis of the tetragonal prismatic nanocapsules used and encapsulation of C60⊂[10]CPP.
Fig. 3: Structural characterization of the matryoshka-like ensemble and its reactivity towards selective formation of Bingel trans-3 bis-adducts.
Fig. 4: Crystal structure of the encapsulated trans-3 bis-adducts and void analysis study on the impact of the different bis-adduct sterics.

Data availability

All data generated or analysed during this study are included in this published article (and its supplementary information files). Crystallographic data for the structures reported in this article have been deposited at the Cambridge Crystallographic Data Centre, under deposition numbers CCDC 1984575 (C60⊂[10]CPP⊂7·(BArF)8), 1984576 (trans-3-(1-C60)⊂[10]CPP⊂6·(BArF)8) and 1984937 ([Cu2(Me2pTp)(OTf)2](OTf)2). Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/.

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Acknowledgements

This work was supported by grants from MINECO-Spain (CTQ2016-77989-P and PID2019-104498GB-I00 to X.R., RTI2018-095622-B-100 to D.M. and I.I., and EUR2019-103824 to F.G.), Generalitat de Catalunya (2017SGR264 and a PhD grant to C.F.-E.) and the Severo Ochoa Center of Excellence Program (Catalan Institute of Nanoscience and Nanotechnology, grant SEV-2017-0706). X.R. is also grateful for ICREA-Acadèmia awards. M.v.D. is grateful for financial support from the Deutsche Forschungsgemeinschaft (project number 182849149-SFB953 ‘Synthetic Carbon Allotropes’), the Fonds der Chemischen Industrie (FCI), the University of Ulm and the Deutscher Akademischer Austauschdienst (PhD fellowship to O.B.). E.U. thanks Universitat de Girona for a PhD grant and we thank Serveis Tècnics de Recerca, Universitat de Girona for technical support. We thank A. Lledó for artwork assistance and H. Maid (Friedrich-Alexander-Universität Erlangen-Nürnberg, Germany) for assistance with cryoprobe NMR spectroscopy.

Author information

Authors and Affiliations

  1. Institut de Química Computacional i Catàlisi and Departament de Química, Universitat de Girona, Girona, Spain

    Ernest Ubasart, Carles Fuertes-Espinosa, Cristina García-Simón & Xavi Ribas

  2. Institute of Organic Chemistry, Ulm University, Ulm, Germany

    Oleg Borodin, Youzhi Xu & Max von Delius

  3. Serveis Tècnics de Recerca, Universitat de Girona, Girona, Spain

    Laura Gómez

  4. ALBA Synchrotron, Cerdanyola del Vallès, Spain

    Judith Juanhuix

  5. Materials Science Institute of Madrid, Spanish National Research Council, Madrid, Spain

    Felipe Gándara

  6. Catalan Institute of Nanoscience and Nanotechnology, CSIC and The Barcelona Institute of Science and Technology, Barcelona, Spain

    Inhar Imaz & Daniel Maspoch

  7. ICREA, Barcelona, Spain

    Daniel Maspoch

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  1. Ernest Ubasart
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Contributions

E.U., C.F.-E. and C.G.-S. performed all self-assembly as well as fullerene functionalization experiments and isolated all products. O.B. performed all spectroscopic host–guest titrations and analysed the results with M.v.D. Y.X. synthesized a batch of [10]CPP and the bromomalonate Bingel reagents. L.G. provided technical assistance on HRMS studies. J.J., I.I., F.G. and D.M. technically assisted, performed and solved the XRD structure of C60⊂[10]CPP⊂7·(BArF)8 and trans-3-(1-C60)⊂[10]CPP⊂7·(BArF)8 at the ALBA synchrotron. M.v.D., C.F. and X.R. conceived the project idea. M.v.D and X.R. wrote the manuscript. X.R. directed the project.

Corresponding authors

Correspondence to Max von Delius or Xavi Ribas.

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The authors declare no competing interests.

Additional information

Peer review information Nature Chemistry thanks T. Barendt, E. Peris and the other, anonymous reviewer(s), for their contribution to the peer review of this work.

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Extended data

Extended Data Fig. 1 Self-assembled tetragonal prismatic nanocapsules.

Self-assembly of the Zn-TCPP and the bimetallic macrocyclic clips [M2(Me2p)]4+, [M2(Me2pp)]4+ and [M2(Me2pTp)]4+, to afford the corresponding tetragonal prismatic nanocapsules with increasing cavity-size, that is, 3·(BArF)8, 4·(BArF)8, 5·(BArF)8, 6·(BArF)8, 7·(BArF)8.

Supplementary information

Supplementary Information

Supplementary Figs. 1–96 and Tables 1–17.

Supplementary Data

CIF file for clip complex [Cu2(Me2pTp)(OTf)2](OTf)2 (CCDC reference 1984937).

Supplementary Data

CIF file for C60⊂[10]CPP⊂7·(BArF)8 (CCDC reference 1984575).

Supplementary Data

CIF file for trans-3-(1-C60)⊂[10]CPP⊂7·(BArF)8 (CCDC reference 1984576).

Supplementary Video

Video summary of the article, containing the video representation of the matryoshka-like crystal structure and the selectivity for the trans-3 C60 bis-adduct.

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Ubasart, E., Borodin, O., Fuertes-Espinosa, C. et al. A three-shell supramolecular complex enables the symmetry-mismatched chemo- and regioselective bis-functionalization of C60. Nat. Chem. 13, 420–427 (2021). https://doi.org/10.1038/s41557-021-00658-6

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