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Assembly of a metal–organic framework by sextuple intercatenation of discrete adamantane-like cages

Nature Chemistry volume 2, pages 461–465 (2010)Cite this article

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Abstract

Metal–organic frameworks form a unique class of multifunctional hybrid materials and have myriad applications, including gas storage and catalysis. Their structure is usually achieved through the infinite coordination of metal ions and multidentate organic ligands by means of strong covalent bonds. Threaded molecules such as catenanes and rotaxanes have largely been restricted to comprising components of two-dimensional interlocking rings or polygons. There are very few examples of the catenation of polyhedral cages. Although it has been postulated that the infinite extended architecture can be obtained from the polycatenation of a discrete cage based on such threading, this has not been documented to date. Here we describe an infinite three-dimensional metal–organic framework composed of catenated polyhedral cages, in which the framework is achieved by mechanical interlocking of all of the vertices of the cages. The three-dimensional polycatenated framework shows twofold self-interpenetration in its crystal packing. The penetration of polycatenanes creates nanosized voids into which the Keggin polyoxometalate anions are perfectly accommodated as counteranions.

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Figure 1: Schematic representation of the details of the adamantane-like {Ag24(trz)18}6+ nanocage.
Figure 5: Arrangement of polyoxometalates and {Ag24(trz)18}6+ nanocages.
Figure 2: Schematic representation of the overall structure of the polycatenanes in 1 from a discrete {Ag24(trz)18}6+ nanocage to three-dimensional infinite polycatenation.
Figure 3: Supramolecular architecture of adjacent interlocking {Ag24(trz)18}6+ nanocages.
Figure 4: Topological views of the twofold interpenetration of the polycatenation in 1.

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  • 24 May 2010

    An incorrect version of Fig. 1 appeared temporarily in this HTML Article in the June issue. This has now been corrected; it is correct in the PDF and in print.

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Acknowledgements

This work was supported by the 973 Key Program of the Ministry of Science and Technology of China (2006CB932904, 2007CB815304 and 2010CB933501), the National Natural Science Foundation of China (20873150, 50772113, 20821061 and 20973173), the Chinese Academy of Sciences (KJCX2-YW-M05, 319) and the National Science Foundation (CHE-0845829; J.P.D.).

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Authors and Affiliations

  1. State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, Fujian, China

    Xiaofei Kuang, Xiaoyuan Wu, Rongmin Yu, Jinshun Huang & Can-Zhong Lu

  2. Department of Chemistry, Tulane University, 6400 Freret Street, New Orleans, 70118, Louisiana, USA

    James P. Donahue

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  1. Xiaofei Kuang
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Contributions

X.K. and C.Z.L. conceived and designed the experiments. X.K. performed the experimental work. X.K., X.W., R.Y., J.H. and C.Z.L. analysed the X-ray structural data and interpreted the results. C.Z.L. was responsible for the overall design, direction and supervision of the project. X.K., R.Y., J.P.D. and C.Z.L. co-wrote the paper.

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Correspondence to Can-Zhong Lu.

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Crystallographic data for compound 1 (CIF 15 kb)

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Kuang, X., Wu, X., Yu, R. et al. Assembly of a metal–organic framework by sextuple intercatenation of discrete adamantane-like cages. Nature Chem 2, 461–465 (2010). https://doi.org/10.1038/nchem.618

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