Exploring cooperative porosity in organic cage crystals using in situ diffraction and molecular simulations

A porous organic cage crystal, α-CC2, shows unexpected adsorption of sulphur hexafluoride (SF₆) in its cage cavities: analysis of the static crystal structure indicates that SF₆ is occluded, as even the smallest diatomic gas, H₂, is larger than the window of the cage pore. Herein, we use in situ powder X-ray diffraction (PXRD) experiments to provide unequivocal evidence for the presence of SF₆ inside the 'occluded' cage voids, pointing to a mechanism of dynamic flexibility of the system. By combining PXRD results with molecular dynamics simulations, we build a molecular level picture of the cooperative porosity in α-CC2 that facilitates the passage of SF₆ into the cage voids.