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Spontaneous assembly of ten components into two interlocked, identical coordination cages

Nature volume 400, pages 52–55 (1999)Cite this article

Abstract

Supermolecules consisting of interlinked ring-like molecules (catenanes)1 are an interesting target for chemical synthesis both for their intrinsic interest as non-covalently bound but robust assemblies and because of the perspective they offer on materials chemistry2. Catenanes have been prepared by metal-ion templating3,4 and self-assembly through other non-covalent interactions5,6,7,8,9,10,11,12. Here we report the synthesis of a catenane composed not of two interlocking rings but of two cages. This structure is prepared by metal-mediated self-assembly13,14,15. The framework of each cage is assembled from five components: two tridentate ligands held together with three metal ions. Because each cage framework can bind an aromatic ring, two cage units will bind one another during their assembly process through the formation of a quadruple aromatic stack, giving rise to the ten-component interlocked supermolecule16,17.

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Figure 1: Assembly of the interlocked-cage complex.
Figure 2: Structure of the interlocked-cage complex.
Figure 3: NMR spectra of 5a (panel a) and 5b (panel b) (500 MHz, D2O, aromatic region).
Figure 4: Formation of 5b via reorganization from 6 and 7.

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References

  1. Wasserman, E. The preparation of interlocking rings: a catenane. J. Am. Chem. Soc. 82, 4433–4434 (1960).

    Article  CAS  Google Scholar 

  2. Amabilino, D. B. & Stoddart, J. F. Interlocked and intertwined structures and superstructures. Chem. Rev. 95, 2725–2728 (1995).

    Article  CAS  Google Scholar 

  3. Dietrich-Buchecker, C. O., Sauvage, J.-P. & Kintzinger, J.-P. Une nouvelle famille de molecules: les metallo-catenanes. Tetrahedr. Lett. 24, 5095–5098 (1983).

    Article  CAS  Google Scholar 

  4. Sauvage, J.-P., Dietrich-Buchecker, C. O. & Chambron, J.-C. in Comprehensive Supramolecular Chemistry Vol. 2(eds Sauvage, J.-P. & Hosseini, M. W.) Ch. 2, 43–83 (Pergamon, Oxford, (1995).

    Google Scholar 

  5. Ashton, P. R. et al . A[2]catenane made to order. Angew. Chem. Int. Edn Engl. 28, 1396–1399 (1989).

    Article  Google Scholar 

  6. Hunter, C. A. Synthesis and structure elucidation of a new [2]-catenane. J. Am. Chem. Soc. 114, 5303–5311 (1992).

    Article  CAS  Google Scholar 

  7. Vögtle, F., Meier, S. & Hoss, R. One-step synthesis of a fourfold functionalized catenane. Angew. Chem. Int. Edn Engl. 31, 1619–1621 (1992).

    Article  Google Scholar 

  8. Fujita, M., Ibukuro, F., Hagihara, H. & Ogura, K. Quantitative self-assembly of a [2] catenane from two preformed molecular rings. Nature 367, 720–723 (1994).

    Article  ADS  CAS  Google Scholar 

  9. Johnston, A. G., Leigh, D. A., Pritchard, R. J. & Deegan, M. D. Facile synthesis and solid-state structure of a benzylic amide [2] catenane. Angew. Chem. Int. Edn Engl. 34, 1209–1212 (1995).

    Article  CAS  Google Scholar 

  10. Hamilton, DG. et al . Tandem hetero-catenation: templating and self-assembly in the mutual closure of two different interlocking rings. J. Am. Chem. Soc. 120, 1096–1097 (1998).

    Article  CAS  Google Scholar 

  11. Batten, S. R. & Robson, R. Interpenetrating nets: ordered, periodic entanglement. Angew. Chem. Int. Edn Engl. 37, 1460–1494 (1998).

    Article  Google Scholar 

  12. Drain, C. M., Nifiatis, F., Vasenko, A. & Batteas, J. D. Prophyrin tessellation by design: metal-mediated self-assembly of large arrays and tapes. Angew. Chem. Int. Edn Engl. 37, 2344–2347 (1998).

    Article  CAS  Google Scholar 

  13. Baxter, P. N. W. in Comprehensive Supramolecular Chemistry Vol. 9(eds Sauvage, J.-P. & Hosseini, M.W.) Ch. 5, 165–211 (Pergamon, Oxford, (1996).

    Google Scholar 

  14. Fujita, M. Self-assembly of [2]catenanes containing metals in their backbones. Acc. Chem. Res. 32, 53–61 (1999).

    Article  CAS  Google Scholar 

  15. Fujita, M. Metal-directed self-assembly of two- and three-dimensional synthetic receptors. Chem. Soc. Rev. 27, 417–425 (1998).

    Article  CAS  Google Scholar 

  16. Dietrich-Buchecker, C., Frommberger, B., Lüer, I., Sauvage, J.-P. & Vögtle, F. Multiring catenanes with a macrobicyclic core. Angew. Chem. Int. Edn Engl. 32, 1434–1437 (1993).

    Article  Google Scholar 

  17. Ashton, P. R. et al . An interwoven supramolecular cage. Angew. Chem. Int. Edn Engl. 36, 59–62 (1997).

    Article  CAS  Google Scholar 

  18. Fujita, M., Aoyagi, M., Ibukuro, F., Ogura, K. & Yamaguchi, K. Made-to-order assembling of [2]catenanes from palladium(II)-linked rectangular molecular boxes. J. Am. Chem. Soc. 120, 611–612 (1998).

    Article  CAS  Google Scholar 

  19. Ibukuro, F., Kusukawa, T. & Fujita, M. Athermally switchable molecular lock. Guest-templated synthesis of a kinetically stable nano-sized cage. J. Am. Chem. Soc. 120, 8561–8562 (1998).

    Article  CAS  Google Scholar 

  20. Jorgensen, W. L. & Severance, D. L. Aromatic-aromatic interactions: free energy profiles for the benzene dimer in water, chloroform, and benzene. J. Am. Chem. Soc. 112, 4768–4774 (1990).

    Article  CAS  Google Scholar 

  21. Hunter, C. A. & Sanders, L. K. M. The nature of π-π interactions. J. Am. Chem. Soc. 112, 5525–5534 (1990).

    Article  CAS  Google Scholar 

  22. Fujita, M. et al . Self-assembly of ten molecules into nanometre-sized organic host frameworks. Nature 378, 469–471 (1995).

    Article  ADS  CAS  Google Scholar 

  23. Hasenknopf, B., Lehn, J.-M., Kneisel, B. O., Baum, G. & Fenske, D. Self-assembly of a circular double helicate. Angew. Chem. Int. Edn Engl. 35, 1838–1840 (1996).

    Article  CAS  Google Scholar 

  24. Fujita, M., Nagao, S. & Ogura, K. Guest-induced organization of a three-dimensional palladium (II) cagelike complex, a prototype for “induced-fit” molecular recognition. J. Am. Chem. Soc. 117, 1649–1650 (1995).

    Article  CAS  Google Scholar 

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Author notes

  1. Makoto Fujita

    Present address: School of Engineering, Nagoya University, Chikusa-ku, Nagoya, 464-8603, Japan

Authors and Affiliations

  1. Coordination Chemistry Laboratories, Institute for Molecular Science, and CREST, Japan Science and Technology Corporation (JST), Myodaiji, 444-8585, Okazaki, Japan

    Makoto Fujita

  2. Graduate University for Advanced Studies, Myodaiji, 444-8585, Okazaki, Japan

    Norifumi Fujita

  3. Department of Applied Chemistry, Faculty of Engineering, Chiba University, Chiba, Yayoicho, 263-8522, Inageku, Japan

    Katsuyuki Ogura

  4. Chemical Analysis Center, Chiba University, Chiba, Yayoicho, 263-8522, Inageku, Japan

    Kentaro Yamaguchi

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  1. Makoto Fujita
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  2. Norifumi Fujita
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  3. Katsuyuki Ogura
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  4. Kentaro Yamaguchi
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Correspondence to Makoto Fujita.

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Fujita, M., Fujita, N., Ogura, K. et al. Spontaneous assembly of ten components into two interlocked, identical coordination cages. Nature 400, 52–55 (1999). https://doi.org/10.1038/21861

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