Guest transport in a nonporous organic solid via dynamic van der Waals cooperativity.

A well-known organic host compound undergoes single-crystal-to-single-crystal phase transitions upon guest uptake and release. Despite a lack of porosity of the material, guest transport through the solid occurs readily until a thermodynamically stable structure is achieved. In order to actively facilitate this dynamic process, the host molecules undergo significant positional and/or orientational rearrangement. This transformation of the host lattice is triggered by weak van der Waals interactions between the molecular components. In order for the material to maintain its macroscopic integrity, extensive cooperativity must exist between the molecules throughout the crystal, such that rearrangement can occur in a well-orchestrated fashion. We demonstrate here that even weak dispersive forces can exert a profound influence over solid-state dynamics.