Nanoporous molecular frameworks1,2,3,4,5,6,7 are important in applications such as separation, storage and catalysis. Empirical rules exist for their assembly but it is still challenging to place and segregate functionality in three-dimensional porous solids in a predictable way. Indeed, recent studies of mixed crystalline frameworks suggest a preference for the statistical distribution of functionalities throughout the pores7 rather than, for example, the functional group localization found in the reactive sites of enzymes8. This is a potential limitation for ‘one-pot’ chemical syntheses of porous frameworks from simple starting materials. An alternative strategy is to prepare porous solids from synthetically preorganized molecular pores9,10,11,12,13,14,15. In principle, functional organic pore modules could be covalently prefabricated and then assembled to produce materials with specific properties. However, this vision of mix-and-match assembly is far from being realized, not least because of the challenge in reliably predicting three-dimensional structures for molecular crystals, which lack the strong directional bonding found in networks. Here we show that highly porous crystalline solids can be produced by mixing different organic cage modules that self-assemble by means of chiral recognition. The structures of the resulting materials can be predicted computationally16,17, allowing in silico materials design strategies18. The constituent pore modules are synthesized in high yields on gram scales in a one-step reaction. Assembly of the porous co-crystals is as simple as combining the modules in solution and removing the solvent. In some cases, the chiral recognition between modules can be exploited to produce porous organic nanoparticles. We show that the method is valid for four different cage modules and can in principle be generalized in a computationally predictable manner based on a lock-and-key assembly between modules.

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  1. 1.

    , , , & Three-dimensional framework with channeling cavities for small molecules: {M2(4,4-bpy)3(NO3)4·xH2O}n (M = Co, Ni, Zn). Angew. Chem. Int. Edn Engl. 36, 1725–1727 (1997)

  2. 2.

    , , & Design and synthesis of an exceptionally stable and highly porous metal–organic framework. Nature 402, 276–279 (1999)

  3. 3.

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

  4. 4.

    et al. Hysteretic adsorption and desorption of hydrogen by nanoporous metal-organic frameworks. Science 306, 1012–1015 (2004)

  5. 5.

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

  6. 6.

    et al. Porous, crystalline, covalent organic frameworks. Science 310, 1166–1170 (2005)

  7. 7.

    et al. Multiple functional groups of varying ratios in metal-organic frameworks. Science 327, 846–850 (2010)

  8. 8.

    et al. Enzyme structure with two catalytic sites for double-sieve selection of substrate. Science 280, 578–582 (1998)

  9. 9.

    Crystal porosity and the burden of proof. Chem. Commun. 1163–1168 (2006)

  10. 10.

    , & Storage of methane and freon by interstitial van der Waals confinement. Science 296, 2367–2369 (2002)

  11. 11.

    , , & Reticular chemistry of metal-organic polyhedra. Angew. Chem. Int. Ed. 47, 5136–5147 (2008)

  12. 12.

    et al. Porous organic cages. Nature Mater. 8, 973–978 (2009)

  13. 13.

    , , , & Heme-like coordination chemistry within nanoporous molecular crystals. Science 327, 1627–1630 (2010)

  14. 14.

    et al. On–off porosity switching in a molecular organic solid. Angew. Chem. Int. Ed. 50, 749–753 (2011)

  15. 15.

    , , & A salicylbisimine cage compound with high surface area and selective CO2/CH4 adsorption. Angew. Chem. Int. Ed. 50, 1046–1055 (2011)

  16. 16.

    et al. Significant progress in predicting the crystal structures of small organic molecules – a report on the fourth blind test. Acta Crystallogr. B 65, 107–125 (2009)

  17. 17.

    Computed crystal energy landscapes for understanding and predicting organic crystal structures and polymorphism. Acc. Chem. Res. 42, 117–126 (2009)

  18. 18.

    , & Addressing chemical diversity by employing the energy landscape concept. Acta Crystallogr. A 66, 518–534 (2010)

  19. 19.

    , , , & Framework functionalisation triggers metal complex binding. Chem. Commun. 2680–2682 (2008)

  20. 20.

    Supramolecular synthons in crystal engineering – a new organic-synthesis. Angew. Chem. Int. Edn Engl. 34, 2311–2327 (1995)

  21. 21.

    , & Use of hydrogen bonds to control molecular aggregation. Self-assembly of three-dimensional networks with large chambers. J. Am. Chem. Soc. 113, 4696–4698 (1991)

  22. 22.

    Engineering crystals by the strategy of molecular tectonics. Chem. Commun. 5830–5837 (2005)

  23. 23.

    , , & Molecular encapsulation. Angew. Chem. Int. Ed. 41, 1488–1508 (2002)

  24. 24.

    Nanoporous molecular crystals. J. Mater. Chem. 20, 10588–10597 (2010)

  25. 25.

    , , & Quasiracemic materials – rediscovering Pasteur’s quasiracemates. Angew. Chem. Int. Ed. 47, 78–81 (2008)

  26. 26.

    & Supramolecular motifs: sextuple aryl embraces in crystalline M(2,2′-bipy)3 and related complexes. Dalton Trans. 1341–1350 (1998)

  27. 27.

    , & Beyond the isotropic atom model in crystal structure prediction of rigid molecules: atomic multipoles versus point charges. Cryst. Growth Des. 5, 1023–1033 (2005)

  28. 28.

    et al. Modelling organic crystal structures using distributed multipole and polarizability-based model intermolecular potentials. Phys. Chem. Chem. Phys. 12, 8478–8490 (2010)

  29. 29.

    & Ab initio crystal structure prediction. II. Flexible molecules. Mol. Phys. 105, 273–291 (2007)

  30. 30.

    , & Pseudoracemic amino acid complexes: blind predictions for flexible two-component crystals. Phys. Chem. Chem. Phys. 12, 8466–8477 (2010)

  31. 31.

    et al. Quickstep: fast and accurate density functional calculations using a mixed Gaussian and plane waves approach. Comp. Phys. Comm. 167, 103–108 (2005)

  32. 32.

    , , & A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J. Chem. Phys. 132, 154104 (2010)

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We thank EPSRC (EP/H000925/1) and the Dutch Polymer Institute for funding. The UK national high-performance computing service HECToR was used for this work through the HPC Materials Chemistry Consortium (EPSRC grant EP/F067496. A.I.C. and G.M.D. are Royal Society Wolfson Merit Award holder and A.T. and G.M.D. are Royal Society University Research Fellows.

Author information


  1. Department of Chemistry and Centre for Materials Discovery, University of Liverpool, Crown Street, Liverpool L69 7ZD, UK

    • James T. A. Jones
    • , Tom Hasell
    • , Xiaofeng Wu
    • , John Bacsa
    • , Kim E. Jelfs
    • , Marc Schmidtmann
    • , Samantha Y. Chong
    • , Dave J. Adams
    • , Abbie Trewin
    • , Alexander Steiner
    •  & Andrew I. Cooper
  2. Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, UK

    • Florian Schiffman
    • , Furio Cora
    •  & Ben Slater
  3. Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, UK

    • Graeme M. Day


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J.T.A.J. prepared cage modules and co-crystals thereof, contributed to powder X-ray diffraction analysis, carried out high-throughput co-crystallization screening experiments and generally coordinated the experimental work; T.H. prepared cage modules and co-crystals and the nanocrystals of (3-S, 3-R), and carried out microscopy; J.T.A.J. and T.H. did the gas sorption analysis; X.W. synthesized module 5; D.J.A. contributed to the cage synthesis; J.B., M.S., S.Y.C. and A.S. performed the crystallography; K.E.J., A.T., F.C. and B.S. performed molecular and periodic simulations, in particular the DFT studies; G.M.D. led the crystal structure prediction; and A.I.C. designed the project and wrote the paper with contributions from all co-authors.

Competing interests

The authors declare no competing financial interests.

Corresponding author

Correspondence to Andrew I. Cooper.

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  1. 1.

    Supplementary Information

    The file contains Supplementary Text, Supplementary Table 1, Supplementary Figures 1-26 with legends and additional references.


  1. 1.

    Supplementary Movie 1

    The movie shows the effect of mixing a solution of cage 3-R with an equivalent solution of cage 3-S - see ‘Figure 27’ legend in Supplementary Information file.

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