Porous materials are important in a wide range of applications including molecular separations and catalysis. We demonstrate that covalently-bonded molecular organic cages can assemble into crystalline microporous materials.1 The porosity is prefabricated in the molecular cage structure and how they are packed within the crystal lattice, as opposed to being formed by self assembly of non-porous sub-units. The ability to dissolve molecular cages in common solvents enables their conversion by re-crystallisation to produce either porous or non-porous polymorphs. We show that a crystalline porous organic cage molecules, can be interconverted between three polymorphic forms (a, �, ?) while retaining long-range crystalline order using solvent vapour. The ability to switch from non-porous to porous polymorphs using solvent vapour is unprecedented in organic molecules and suggests a design principle for responsive organic switches where porosity can be turned on and off. (1)        Tozawa, T. et. al. Nat. Mater. 2009, 8, 973.

Boolean solid-state porosity switching in a molecular organic solid

240th National Meeting (2010)

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