Abstract
Two porous organic cages with different thermodynamic polymorphs were induced by co-solvents to interchange their crystal packing modes, thus achieving guest-mediated control over solid-state porosity. In situ crystallography allows the effect of the co-solvent guests on these structural interconversions to be understood.
Highlights
Two porous organic cages with different thermodynamic polymorphs were induced by co-solvents to interchange their crystal packing modes, achieving guest-mediated control over solid-state porosity
In situ crystallography allows the effect of the co-solvent guests on these structural interconversions to be understood
We have developed porous organic cage molecules via [4+6] cycloimination reactions of 1,3,5-triformylbenzene (TFB) with vicinal aliphatic diamines such as (1R,2R)-diaminocyclohexane (CC3-R) and (1R,2R)-diaminocyclopentane (CC4-R) (Fig. 1a).[5]
Summary
Two porous organic cages with different thermodynamic polymorphs were induced by co-solvents to interchange their crystal packing modes, achieving guest-mediated control over solid-state porosity. The inclusion of Et2O during crystallisation disrupts the otherwise favourable window-to-window CC3-R cage pairing, as found in CC3a, which has a cage–cage intermolecular interaction energy calculated to be around 150 kJ molÀ1 (DFT-D3).[7] the three cage windows pack in a relatively inefficient manner, forming three extrinsic cavities into which the methyl termini of the Et2O solvent molecules are directed (Fig. 2).
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