Revealing Disorder, Sorption Locations and a Sorption-Induced Single Crystal-Single Crystal Transformation in a Rare-Earth fcu-Type Metal-Organic Framework

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 mu 3-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 Fm3m (for MeOH(l), N2(g), CO2(g or l)) to cubic Pa3 (for DMF(l)/H2O(l)) symmetry with retention of the fcu topology, and conversion between the Pa3 and Fm3m 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.