Coordination modulated on-off switching of flexibility in a metal-organic framework

Stimuli-responsive metal-organic frameworks (MOFs) exhibit dynamic, and typically reversible, structural changes upon exposure to external stimuli. This process often induces drastic changes in their adsorption properties. Herein, we present a stimuli-responsive MOF, 1 ·[CuCl], that shows temperature dependent switching from a rigid to flexible phase. This conversion is associated with a dramatic reversible change in the gas adsorption properties, from Type-I to S-shaped isotherms. The structural transition is facilitated by a novel mechanism that involves both a change in coordination number (3 to 2) and geometry (trigonal planar to linear) of the post-synthetically added Cu( i ) ion. This process serves to 'unlock' the framework rigidity imposed by metal chelation of the bis-pyrazolyl groups and realises the intrinsic flexibility of the organic link. Stimuli-responsive metal-organic frameworks (MOFs) exhibit dynamic structural changes upon exposure to external stimuli. Here the coordination geometry of a post-synthetically added metal ion drastically changes the adsorption properties.