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

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 μ₃–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 ¹⁹F NMR characterization of 2,5-dihydroxyterepthalic acid (Y-DOBDC) MOF synthesized with a fluorine-containing modulator. ¹⁹F 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 ¹⁹F 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 (SO₂, NO₂, H₂O) 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 (SO₂ > H₂O > NO₂). 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.