Metal-Organic Frameworks Featuring 18-Connected Nonanuclear Rare-Earth Oxygen Clusters and Cavities for Efficient C₂H₂/CO₂ Separation

Two rare-earth (RE) metal-organic frameworks (MOFs) formulated as {(Me2NH2)(2)[RE9(mu(3)-OH)8(mu(2)-OH)(3)(DCPB)(6)(H2O)(3)]}(n) (RE = Y3+ and Tb3+; termed JXNU-10) built from a triangular 3,5-di(4'-carboxylphenyl)benzoic acid (DCPB3-) ligand are presented. JXNU-10 features the rarely observed 18-connected nonanuclear [RE9(mu(3)-OH)(8)(mu(2)-OH)(3)] clusters, one-dimensional-nanosized tubular channels, and trigonalbipyramidal cavities. The presence of the high-nuclear RE-oxo clusters and the robust coordination bonds between the highly charged RE ions and the hard base of the carboxylate/hydroxyl oxygen atoms yielded the water-resistant JXNU-10 materials. JXNU-10 exhibits highly selective sorption of C2H2 over CO2 and highly efficient separation of a C2H2 and CO2 mixture. The carboxylate oxygen atoms and the rich pi systems of the organic ligands on the pore walls are the desirable binding sites for a C2H2 molecule with acidic hydrogen atoms and an alkyne group, facilitating the excellent efficiency of JXNU-10 for C2H2/CO2 separation demonstrated by breakthrough experiments.