Design and synthesis of an exceptionally stable and highly porous metal-organic framework

Abstract

Open metal–organic frameworks are widely regarded as promising materials for applications1,2,3,4,5,6,7,8,9,10,11,12,13,14,15 in catalysis, separation, gas storage and molecular recognition. Compared to conventionally used microporous inorganic materials such as zeolites, these organic structures have the potential for more flexible rational design, through control of the architecture and functionalization of the pores. So far, the inability of these open frameworks to support permanent porosity and to avoid collapsing in the absence of guest molecules, such as solvents, has hindered further progress in the field14,15. Here we report the synthesis of a metal–organic framework which remains crystalline, as evidenced by X-ray single-crystal analyses, and stable when fully desolvated and when heated up to 300?°C. This synthesis is achieved by borrowing ideas from metal carboxylate cluster chemistry, where an organic dicarboxylate linker is used in a reaction that gives supertetrahedron clusters when capped with monocarboxylates. The rigid and divergent character of the added linker allows the articulation of the clusters into a three-dimensional framework resulting in a structure with higher apparent surface area and pore volume than most porous crystalline zeolites. This simple and potentially universal design strategy is currently being pursued in the synthesis of new phases and composites, and for gas-storage applications.

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Figure 1: Construction of the MOF-5 framework.
Figure 2: Representation of a {100} layer of the MOF-5 framework shown along the a-axis (C, grey; O, green).
Figure 3: Nitrogen gas sorption isotherm at 78?K for MOF-5 (filled circles, sorption; open circles desorption).

References

  1. 1

    Kinoshita,Y., Matsubara,I., Higuchi,T. & Saito,Y. The crystal structure of bis(adiponitrilo) copper(I) nitrate. Bull. Chem. Soc. Jpn 32, 1221–1226 (1959).

    CAS  Article  Google Scholar 

  2. 2

    Kitgawa,S., Munakata,M. & Tanimura,T. Tetranuclear copper(I)-based infinite one-dimensional chain complex. Chem. Lett. 623–626 (1991).

  3. 3

    Abrahams,B. F., Hoskins,B. F. & Robson,R. Infinite polymeric frameworks consisting of three dimensionally linked rod-like segments. J. Am. Chem. Soc. 113, 3606–3607 (1991).

    CAS  Article  Google Scholar 

  4. 4

    Zaworotko,M. J. Cooperative bonding affords a holesome story. Nature 386, 220–221 (1997).

    ADS  CAS  Article  Google Scholar 

  5. 5

    Fagan,P. J. & Ward,M. D. Building molecular crystals. Sci. Am. 267, 48–54 (1992).

    ADS  CAS  Article  Google Scholar 

  6. 6

    Carlucci,L., Ciani,G., Proserpio,D. M. & Sironi,A. Interpenetrating diamondoid frameworks of silver(I) cations linked by N,N′-bidentate molecular rods. J. Chem. Soc. Chem. Commun. 2755–2756 (1994).

  7. 7

    Mallouk,T. E. Crowns get organized. Nature 387, 350–351 (1997).

    ADS  CAS  Article  Google Scholar 

  8. 8

    Gardner,G. B., Venkataraman,D., Moore,J. S. & Lee,S. Spontaneous assembly of a hinged coordination network. Nature 374, 792–795 (1995).

    ADS  CAS  Article  Google Scholar 

  9. 9

    Yaghi,O. M., Li,G. & Li,H. Selective binding and removal of guests in a microporous metal-organic framework. Nature 378, 703–706 (1995).

    ADS  CAS  Article  Google Scholar 

  10. 10

    Lu,J. et al. Coordination polymers of Co(NCS)2 with pyrazine and 4,4-bipyridine: syntheses and structures. Inorg. Chem. 36, 923–928 (1997).

    CAS  Article  Google Scholar 

  11. 11

    Vaid,T. P., Lobkovsky,E. B. & Wolczanski,P. T. Covalent 3- and 2-dimensional titanium-quinone networks. J. Am. Chem. Soc. 119, 8742–8743 (1997).

    CAS  Article  Google Scholar 

  12. 12

    Liu,F. Q. & Tilley,T. D. A coordination network based on d0 transition-metal centers: synthesis and structure of the [2,4]-connected layered compound [(TiCl4)2Si(C6H4CN-p)4]·1.5C7H8. J. Chem. Soc. Chem. Commun. 103–104 (1998).

  13. 13

    MacGillivray,L. R., Groeneman,R. H. & Atwood,J. L. Design and self-assembly of cavity-containing rectangular grids. J. Am. Chem. Soc. 120, 2676–2677 (1998).

    CAS  Article  Google Scholar 

  14. 14

    Yaghi,O. M., Li,H., Davis,C., Richardson,D. & Groy,T. L. Synthetic strategies, structure patterns, and emerging properties in the chemistry of modular porous solids. Acc. Chem. Res. 31, 575–585 (1998).

    Article  Google Scholar 

  15. 15

    Kepert,C. J. & Rosseinsky,M. J. Zeolite-like crystal structure of an empty microporous framework. J. Chem. Soc. Chem. Commun. 375–376 (1999).

  16. 16

    Clegg,W. et al. Crystal structures of three basic zinc carboxylates together with infrared and FAB mass spectrometry studies in solution. Inorg. Chim. Acta 186, 51–60 (1991).

    CAS  Article  Google Scholar 

  17. 17

    Harrison,W. T. A. et al. Synthesis and characterization of a new family of thermally stable open framework zincophosphate/arsenate phases: M3Zn4O(XO4)3·nH2O (M = Na,K,Rb,Li,..; X = P,As; n = 3.5–6). Crystal structures of Rb3Zn4O(PO4)·3.5H2O, K3Zn4O(AsO4)3·4H2O, and Na3Zn4O(PO4)3·6H2O. Chem. Mater. 8, 691–700 (1996).

    CAS  Article  Google Scholar 

  18. 18

    Li,H., Eddaouidi,M., Groy,T. L. & Yaghi,O. M. Establishing microporosity in open metal-organic frameworks: gas sorption isotherms for Zn(BDC) (BDC=1,4-benzenedicarboxylate). J. Am. Chem. Soc. 120, 8571–8672 (1998).

    CAS  Article  Google Scholar 

  19. 19

    Breck,D. W. Zeolite Molecular Sieves (Wiley & Sons, New York, 1974).

    Google Scholar 

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Acknowledgements

We thank F. Hollander and R. Staples for X-ray structure determinations. This work was supported by the National Science Foundation (M.O.K. and O.M.Y.), the Department of Energy (O.M.Y.) and Nalco Chemical Company.

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Correspondence to O. M. Yaghi.

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Li, H., Eddaoudi, M., O'Keeffe, M. et al. Design and synthesis of an exceptionally stable and highly porous metal-organic framework. Nature 402, 276–279 (1999). https://doi.org/10.1038/46248

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