Pore Shape Modification of a Microporous Metal-Organic Framework Using High Pressure: Accessing a New Phase with Oversized Guest Molecules

Pressures up to 0.8 GPa have been used to squeeze a range of sterically oversized C5-C8 alkane guest molecules into the cavities of a small-pore Sc-based metal organic framework. Guest inclusion causes a pronounced reorientation of the aromatic rings of one-third of the terephthalate linkers, which act as torsion springs, resulting in a fully reversible change in the local pore structure. The study demonstrates how pressure-induced guest uptake can be used to investigate framework flexibility relevant to breathing behavior and to understand the uptake of guest molecules in MOFs relevant to hydrocarbon separation.