Size-dependent guest-memory switching of the flexible and robust adsorption characteristics of layered metal-organic frameworks.

Flexible-robust metal-organic frameworks (MOFs), which exhibit unique hybrid nature comprising both flexible and rigid framework characteristics, exhibit high potential for hydrocarbon separations. However, no clear guidelines have been established to regulate their hybrid characteristics owing to limited understanding of their adsorption mechanism. This study investigates the effects of the particle size of a flexible-robust MOF on its adsorption and structural transition behaviors. The robust nature originates from the structural transition of a metastable guest-free structure, while its flexible nature arises from another guest-free structure. The type of guest-free structure is predominantly determined by the particle size; particles below the critical size are trapped in the metastable guest-free structure. Notably, the critical size varies with the type of guest molecule to be removed; consequently, the difference in critical size results in guest-memory characteristics, enabling guest-free structure switching. These results underscore the importance of controlling the particle size to fine-tune hybrid adsorption characteristics of flexible-robust MOFs.