Metal-organic frameworks (MOFs), which respond to external stimuli such as guest removal/reintroduction, guest exchange, oxidation, pressure, temperature, and light, vary the chemical or physical properties through the structural rearrangement of their molecular components. Thus, if the transformation occurs in a single-crystal-to-single-crystal (SC-SC) manner, direct observations of structural changes in MOFs are possible through single-crystal X-ray diffraction (SCD). In this context, we present a 3D doubly interpenetrated Zn4O-containing MOF, which exhibits dynamic structural changes upon guest exchange with organic solvents. Particularly, after the immersion in MeOH over 1 week, one of four tetrahedral Zn2+ ions in Zn4O clusters changes its geometry to octahedral ions with two bound MeOH molecules, which could be crystallographically observed. This unique coordination environment of the SBUs leads the MOF to undergo cation exchange and enable its use in catalytic applications. |