Dramatic Enhancement of Rare-Earth Metal–Organic Framework Stability Via Metal Cluster Fluorination

[Image: see text] Rare-earth polynuclear metal–organic frameworks (RE-MOFs) have demonstrated high durability for caustic acid gas adsorption and separation based on gas adsorption to the metal clusters. The metal clusters in the RE-MOFs traditionally contain RE metals bound by μ(3)–OH groups connected via organic linkers. Recent studies have suggested that these hydroxyl groups could be replaced by fluorine atoms during synthesis that includes a fluorine-containing modulator. Here, a combined modeling and experimental study was undertaken to elucidate the role of metal cluster fluorination on the thermodynamic stability, structure, and gas adsorption properties of RE-MOFs. Through systematic density-functional theory calculations, fluorinated clusters were found to be thermodynamically more stable than hydroxylated clusters by up to 8–16 kJ/mol per atom for 100% fluorination. The extent of fluorination in the metal clusters was validated through a (19)F NMR characterization of 2,5-dihydroxyterepthalic acid (Y-DOBDC) MOF synthesized with a fluorine-containing modulator. (19)F magic-angle spinning NMR identified two primary peaks in the isotropic chemical shift (δ(iso)) spectra located at −64.2 and −69.6 ppm, matching calculated (19)F NMR δ(iso) peaks at −63.0 and −70.0 ppm for fluorinated systems. Calculations also indicate that fluorination of the Y-DOBDC MOF had negligible effects on the acid gas (SO(2), NO(2), H(2)O) binding energies, which decreased by only ∼4 kJ/mol for the 100% fluorinated structure relative to the hydroxylated structure. Additionally, fluorination did not change the relative gas binding strengths (SO(2) > H(2)O > NO(2)). Therefore, for the first time the presence of fluorine in the metal clusters was found to significantly stabilize RE-MOFs without changing their acid-gas adsorption properties.