Metal-Organic Frameworks Featuring 18-Connected Nonanuclear Rare-Earth Oxygen Clusters and Cavities for Efficient CH/CO Separation.

Two rare-earth (RE) metal-organic frameworks (MOFs) formulated as {(MeNH)[RE(μ-OH)(μ-OH)(DCPB)(HO)]} (RE = Y and Tb; termed JXNU-10) built from a triangular 3,5-di(4'-carboxylphenyl)benzoic acid (DCPB) ligand are presented. JXNU-10 features the rarely observed 18-connected nonanuclear [RE(μ-OH)(μ-OH)] clusters, one-dimensional-nanosized tubular channels, and trigonal-bipyramidal 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 CH over CO and highly efficient separation of a CH and CO mixture. The carboxylate oxygen atoms and the rich π systems of the organic ligands on the pore walls are the desirable binding sites for a CH molecule with acidic hydrogen atoms and an alkyne group, facilitating the excellent efficiency of JXNU-10 for CH/CO separation demonstrated by breakthrough experiments.