Revealing Disorder, Sorption Locations and a Sorption-Induced Single Crystal-Single Crystal Transformation in a...

Rare-earth metal-organic frameworks (RE-MOFs) formed in the presence of fluoride donors are a group of complex and applicable MOFs. Determining structural complexity is crucial in applying such MOFs and has been achieved to uncover framework disorders in the important fcu framework topology MOF, Y-ndc-fcu-MOF (1). 1 is found to contain F^- groups disordered over the μ₃-face-capping sites in its secondary building unit (SBU) and framework distortions upon sorption of different guest molecules. The favored location of the guests is within the octahedral cage of 1 where they interact with the Y³⁺ centers. The size, shape, and interactions of the different guests lead to subtle distortions within the SBU and adoption of specific orientations of the naphthalene group of the 1,4-naphthalenedicarboxylate framework linkers. The sorption of DMF_(l)/H₂O_(l) lowers the symmetry from cubic Fm3̅m (for MeOH_(l), N_2(g), CO_2(g or l)) to cubic Pa3̅ (for DMF_(l)/H₂O_(l)) symmetry with retention of the fcu topology, and conversion between the Pa3̅ and Fm3̅m structures is induced by solvent exchange. Such disorder and sorption locations and transformation are important considerations during the optimization and application of MOFs for sorption-based technologies.