Skip to main content

Thank you for visiting You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Letter
  • Published:

Controlling interpenetration in metal–organic frameworks by liquid-phase epitaxy


Metal–organic frameworks (MOFs) are highly porous materials generally consisting of two building elements: inorganic coupling units and organic linkers1,2,3,4. These frameworks offer an enormous porosity, which can be used to store large amounts of gases and, as demonstrated in more recent applications5,6, makes these compounds suitable for drug release. The huge sizes of the pores inside MOFs, however, also give rise to a fundamental complication, namely the formation of sublattices occupying the same space. This interpenetration greatly reduces the pore size and thus the available space within the MOF structure7. We demonstrate here that the formation of the second, interpenetrated framework can be suppressed by using liquid-phase epitaxy on an organic template. This success demonstrates the potential of the step-by-step method to synthesize new classes of MOFs not accessible by conventional solvothermal methods.

This is a preview of subscription content, access via your institution

Access options

Buy this article

Prices may be subject to local taxes which are calculated during checkout

Figure 1: Representation of MOF synthesis concepts.
Figure 2: SPR signal as a function of time recorded in situ during sequential injections.
Figure 3: Out-of-plane XRD pattern.
Figure 4: Out-of-plane XRD pattern.
Figure 5: Proposed model structure.

Similar content being viewed by others


  1. Ferey, G. Microporous solids: From organically templated inorganic skeletons to hybrid frameworks... Ecumenism in chemistry. Chem. Mater. 13, 3084–3098 (2001).

    Article  CAS  Google Scholar 

  2. Hoskins, B.-F. & Robson, R. Design and construction of a new class of scaffolding-like materials comprising infinite polymeric frameworks of 3-D-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′,4′′,4′′′-tetracyanotetraphenylmethane]Bf4.Xc6h5no2. J. Am. Chem. Soc. 112, 1546–1554 (1990).

    Article  CAS  Google Scholar 

  3. Kitagawa, S., Kitaura, R. & Noro, S. Functional porous coordination polymers. Angew. Chem. Int. Ed. 43, 2334–2375 (2004).

    Article  CAS  Google Scholar 

  4. Rowsell, J. & Yaghi, O. Metal organic frameworks, a new class of porous materials. Microporous Mesoporous Mater. 73, 3–14 (2004).

    Article  CAS  Google Scholar 

  5. Horcajada, P. et al. Flexible porous metal–organic frameworks for a controlled drug delivery. J. Am. Chem. Soc. 130, 6774–6780 (2008).

    Article  CAS  Google Scholar 

  6. Horcajada, P. et al. Metal–organic frameworks as efficient materials for drug delivery. Angew. Chem. Int. Ed. 45, 5974–5978 (2006).

    Article  CAS  Google Scholar 

  7. Yaghi, O.-M. A tale of two entanglements. Nature Mater. 6, 92–93 (2007).

    Article  CAS  Google Scholar 

  8. Snurr, R.-Q., Hupp, J.-T. & Nguyen, S.-T. Prospects for nanoporous metal–organic materials in advanced separations processes. AICHE J. 50, 1090–1095 (2004).

    Article  CAS  Google Scholar 

  9. Maji, T.-K., Uemura, K., Chang, H.-C., Matsuda, R. & Kitagawa, S. Expanding and shrinking porous modulation based on pillared-layer coordination polymers showing selective guest adsorption. Angew. Chem. Int. Ed. 43, 3269–3272 (2004).

    Article  CAS  Google Scholar 

  10. Seo, J.-S. et al. A homochiral metal–organic porous material for enantioselective separation and catalysis. Nature 404, 982–986 (2000).

    Article  CAS  Google Scholar 

  11. Hermes, S., Schroder, F., Amirjalayer, S., Schmid, R. & Fischer, R.-A. Loading of porous metal–organic open frameworks with organometallic CVD precursors: Inclusion compounds of the type [LnM](a)@MOF-5. J. Mater. Chem. 16, 2464–2472 (2006).

    Article  CAS  Google Scholar 

  12. Hermes, S. et al. Metal@MOF: Loading of highly porous coordination polymers host lattices by metal organic chemical vapor deposition. Angew. Chem. Int. Ed. 44, 6237–6241 (2005).

    Article  CAS  Google Scholar 

  13. Allendorf, M.-D. et al. Stress-induced chemical detection using flexible metal–organic frameworks. J. Am. Chem. Soc. 130, 14404 (2008).

    Article  CAS  Google Scholar 

  14. Shekhah, O. et al. Step-by-step route for the synthesis of metal–organic frameworks. J. Am. Chem. Soc. 129, 15118–15119 (2007).

    Article  CAS  Google Scholar 

  15. Biemmi, E., Scherb, C. & Bein, T. Oriented growth of the metal–organic framework Cu3(BTC)2(H2O)3·xH2O tunable with functionalized self-assembled monolayers. J. Am. Chem. Soc. 129, 8054–8055 (2007).

    Article  CAS  Google Scholar 

  16. Hermes, S., Schröder, F., Chelmowski, R., Wöll, C. & Fischer, R.-A. Selective nucleation and growth of metal–organic open framework thin films on patterned COOH/CF3-terminated self-assembled monolayers on Au(111). J. Am. Chem. Soc. 127, 13744–13745 (2005).

    Article  CAS  Google Scholar 

  17. Ferey, G. et al. A chromium terephthalate-based solid with unusually large pore volumes and surface area. Science 309, 2040–2042 (2005).

    Article  CAS  Google Scholar 

  18. Batten, S.-R. & Robson, R. Interpenetrating nets: Ordered, periodic entanglement. Angew. Chem. Int. Ed. 37, 1460–1494 (1998).

    Article  Google Scholar 

  19. Eddaoudi, M. et al. Modular chemistry: Secondary building units as a basis for the design of highly porous and roboust metal–organic carboxylate frameworks. Acc. Chem. Res. 34, 319–330 (2001).

    Article  CAS  Google Scholar 

  20. Eddaoudi, M. et al. Systematic design of pore size and functionality in isoreticular MOFs and their application in methane storage. Science 295, 469–472 (2002).

    Article  CAS  Google Scholar 

  21. Hafizovic, J. et al. The inconsistency in adsorption properties and powder XRD data of MOF-5 is rationalized by framework interpenetration and the presence of organic and inorganic species in the nanocavities. J. Am. Chem. Soc. 129, 3612–3620 (2007).

    Article  CAS  Google Scholar 

  22. Tranchemontagne, D. J., Hunt, J. R. & Yaghi, O. M. Room temperature synthesis of metal–organic frameworks: MOF-5, MOF-74, MOF-177, MOF-199, and IRMOF-0. Tetrahedron 64, 8553–8557 (2008).

    Article  CAS  Google Scholar 

  23. Chen, B.-L. et al. A microporous metal–organic framework for gas-chromatographic separation of alkanes. Angew. Chem. Int. Ed. 45, 1390–1393 (2006).

    Article  CAS  Google Scholar 

  24. Munuera, C., Shekhah, O., Wang, H., Wöll, C. & Ocal, C. The controlled growth of oriented metal organic frameworks on functionalized surfaces as followed by scanning force microscopy. Phys. Chem. Chem. Phys. 10, 7257–7261 (2008).

    Article  CAS  Google Scholar 

  25. Ma, B.-Q., Mulfort, K.-L. & Hupp, J.-T. Microporous pillared paddle-wheel frameworks based on mixed-ligand coordination of zinc ions. Inorg. Chem. 44, 4912–4914 (2005).

    Article  CAS  Google Scholar 

Download references


We acknowledge financial support by the EU through the FP6 STREP initiative ‘SURMOF’.

Author information

Authors and Affiliations



O.S. and H.W. prepared the SURMOFs investigated in this study. A.T. and B.S. synthesized the organothiols used to fabricate the SAMs. M.P. and C.O. carried out the AFM work. Data analysis was carried out by O.S., D.Z., R.F. and C.W. The work was directed by O.S., R.F. and C.W. All authors contributed equally in writing the manuscript.

Corresponding author

Correspondence to Christof Wöll.

Supplementary information

Supplementary Information

Supplementary Information (PDF 350 kb)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Shekhah, O., Wang, H., Paradinas, M. et al. Controlling interpenetration in metal–organic frameworks by liquid-phase epitaxy. Nature Mater 8, 481–484 (2009).

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI:

This article is cited by


Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing