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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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.
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.
About this article
Nature Reviews Materials (2016)