Conversion of Molecules and Clusters to Extended 3-D Cage and Channel Networks

  • Omar M. Yaghi


Inorganic solids with inner cavities such as zeolites have found widespread use as industrial sorbents, ion-exchangers and shape-selective catalysts due to their ability to reversibly bind small molecules and ions.1 In an effort to explore the possibility of producing zeolite-like materials that are not based on oxides, we and others have prepared coordination solids composed of organic ligands linked to metal ions to give extended structures. Bifunctional rod-like ligands such as, cyanides2 and 4,4′-bipyridyl3 have been utilized as anchors in linking transition metal ions to support the formation of structures with cavities where organic molecules or charge balance ions are accommodated. This synthetic strategy is schematically shown in Figure 1 for the formation of a diamond lattice from a rod like ligand and a metal ion capable of tetrahedral coordination. In principle, an extensive number of other frameworks with diverse topologies may be assembled by choosing the appropriate units of building blocks and guest species.


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1.
    A. Dyer. “An Introduction to Zeolite Molecular Sieves,” Wiley, Chichester (1988).Google Scholar
  2. 2.
    For example: (a) J. Kim, D. Whang, J. I. Lee, and K. Kim, Guest-dependent [Cd(CN)2]n host structures of cadmium cyanide-alcohol clathrates: two new [Cd(CN)2]n frameworks formed with PrnOH and PriOH guests, J. Chem. Soc., Chem. Commun. 1400 (1993). (b) K.-M. Park and T. Iwamoto, Urea- and thiourea-like host structures of catena- [(1,2-diaminopropane)cadmium(II) tetra-µ-cyanonickelate(II)] accommodating aliphatic guests, J. Chem. Soc., Chem. Commun. 72 (1992). (c) B.F. Abrahams, BJF. Hoskins, J. Liu, and R. Robson, The archetype for a new class of simple extended 3D honeycomb frameworks. The synthesis and x-ray crystal structures of Cd(CN) 5/3(OH)1/3•l/3(C 6 H 12 N 4 ), Cd(CN)2•l/3(C6H12N4), and Cd(CN)2•2/3H2O·tBuOH (C6H12N4 = hexamethylenetetramine) revealing two topologically equivalent but geometrically different frameworks, J. Am. Chem. Soc. 113:3045 (1991). (d) B.F. Hoskins and R. Robson, Design and construction of a new class of scaffolding-like materials comprising infinite polymeric frameworks of 3D-linked molecular rods. A reappraisal of the Zn(CN)2 and Cd(CN)2 structures and the synthesis and structure of the diamond-related frameworks [N(CH3)4][CuIZnII(CN)4] and CuI[4,4,44- tetracyanotetraphenylmethane]BF4•xC6H5NO2, J. Am. Chem. Soc., 112:1546 (1990).Google Scholar
  3. 3.
    For example: (a) L.R. MacGillivray, S. Subramanian, and M.J. Zaworotko, Interwoven two- and three- dimensional coordination polymers through self-assembly of CuI cations with linear bidentate ligands, J. Chem. Soc., Chem. Commun. 1325 (1994). (b) O.M. Yaghi, D.A. Richardson, G. Li, C.E. Davis, and T.L. Groy, Open-framework solids with diamond-like structures prepared from clusters and metal-organic building blocks, Mater. Res. Soc. Symp. Proc., in press (1995).Google Scholar
  4. 4.
    T. Kitazawa, H. Sugisawa, M. Takeda, and T. Iwamoto, Structural characterisation of infinite three- dimensional [Cd4(CN)9]_ ion, J. Chem. Soc., Chem. Commun. 1855 (1993), and references therein.Google Scholar
  5. 5.
    B.F. Hoskins and R. Robson, Infinite polymeric frameworks consisting of three dimensionally linked rod-like segments, J. Am. Chem. Soc. 111:5962 (1989).CrossRefGoogle Scholar
  6. 6.
    O.M. Yaghi and G. Li, Presence of mutually interpenetrating sheets and channels in the extended structure of Cu(4, 4-bipyridine)Cl, Angew. Chem., Int. Ed. Engl., in press (1995).Google Scholar
  7. 7.
    (a) O.M Yaghi, G. Li, and T.L. Groy, Conversion of hydrogen-bonded Mn(II) and Zn(II) squarate molecules, chains and sheets to 3-D cage networks, J. Chem. Soc., Dalton Trans., in press (1995). (b) A. Weiss, E. Riegler, and C. Robl, Transition metal squarates, II: On the structure of cubic (MC4O4•2H2O)3•CH3COOH•H2O (M = Zn2+, Ni2+), Z. Naturforsch. 41b:1329 (1986).Google Scholar
  8. 8.
    O.M. Yaghi, Z. Sun, D.A. Richardson, and T.L. Groy, Directed transformation of molecules to solids: synthesis of a microporous sulfide from molecular germanium sulfide cages, J. Am. Chem. Soc. 116:807 (1994).CrossRefGoogle Scholar
  9. 9.
    O.M. Yaghi, G. Li, and T.L. Groy, Preparation of single crystals of coordination solids in silica gels: synthesis and structure of CuII(l,4-C4H4N2)(C4O4)(OH2)4, J. Solid State Chem., in press (1995).Google Scholar
  10. 10.
    X. Wang, M. Simard, and J.D. Wuest, Molecular tectonics. Three-dimensional organic networks with zeolitic properties, J. Am. Chem. Soc. 116:12119 (1994) and references therein.CrossRefGoogle Scholar
  11. 11.
    H.K. Chae, W.G. Klemperer, D.A. Payne, C.T.A. Suchicital, D.R. Wake, and S.R. Wilson, Clathrasils: new materials for nonlinear optical applications, in: “Materials for Nonlinear Optics: Chemical Perspectives,” S.R. Marder, J.E. Sohn, and G.D. Stucky, eds., Publisher, City (1991).Google Scholar

Copyright information

© Springer Science+Business Media New York 1996

Authors and Affiliations

  • Omar M. Yaghi
    • 1
  1. 1.Department of Chemistry and Biochemistry Goldwater Center for Science and EngineeringArizona State UniversityTempeUSA

Personalised recommendations