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Nat Chem. 2014 Feb;7(2):153-9. doi: 10.1038/nchem.2156.

Trapping virtual pores by crystal retro-engineering.

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Department of Chemistry and Centre for Materials Discovery, University of Liverpool, L69 3BX, UK.
Department of Chemistry, Imperial College London, SW7 2AZ, UK.


Stable guest-free porous molecular crystals are uncommon. By contrast, organic molecular crystals with guest-occupied cavities are frequently observed, but these cavities tend to be unstable and collapse on removal of the guests-this feature has been referred to as 'virtual porosity'. Here, we show how we have trapped the virtual porosity in an unstable low-density organic molecular crystal by introducing a second molecule that matches the size and shape of the unstable voids. We call this strategy 'retro-engineering' because it parallels organic retrosynthetic analysis, and it allows the metastable two-dimensional hexagonal pore structure in an organic solvate to be trapped in a binary cocrystal. Unlike the crystal with virtual porosity, the cocrystal material remains single crystalline and porous after removal of guests by heating.


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