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Due to their intrinsic structural features, the design and synthesis of a new type of zeolite-like metal–organic frameworks (ZMOFs) is highly desirable but challenging. Herein, solvothermal reactions between an angular dicarboxylate linker and rare-earth (RE) ions afforded two RE-MOFs, namely, Tb-ZMOF-2 and Tb-ZMOF-3, respectively. Structural analyses reveal that Tb-ZMOF-2 encompasses a novel [446482] cage, while Tb-ZMOF-3 contains nonanuclear (i.e., D6R) and hexanuclear (i.e., D4R) RE clusters simultaneously, subsequently resulting in two new zeolitic topologies. Thanks to its high surface area and pore volume, Tb-ZMOF-2 demonstrates considerably high gravimetric and volumetric methane storage working capacities.

The efficient single-step purification of ethylene from ternary C2mixtures containing ethane and acetylene is challenging and demanding. Herein, we introduce a novel cerium-based metal–organic framework (MOF) of Ce-NTB-rtksynthesized via a ligand-conformer strategy. The Ce-NTB-rtkfeatures a rare tetranuclear cerium cluster and 2D kgdlayers pillared by a 3D rtlframework concomitant with an extraordinary (3,3,12)-c network. The compound encompasses microporous cavities replete with a nonpolar microenvironment. Gas sorption and breakthrough experiments demonstrate its superior affinity for C2H6and C2H2over C2H4, enabling effective single-step ethylene purification. Computational simulations reveal that preferential adsorptions are facilitated by different interaction strengths of C–H···O hydrogen bonds. The performance of Ce-NTB-rtkin separation selectivity and regeneration capacity makes it a promising candidate for sustainable and cost-effective ethylene purification, showcasing the potential of MOFs in advanced gas separation applications.

Design and synthesis of multinary metal–organic frameworks (MOFs) are of paramount importance but challenging. Nevertheless, pore space partitioning has provided a valuable avenue to isolate ternary MOFs bearing advanced gas storage and separation properties. Herein, a rare (3,3,8)-c Fe-BQDC-BTC-TPBTC MOF was constructed by means of solvothermal reaction between iron ions, a zigzag dicarboxylate H2BQDC ligand and another two C3-symmetry TPBTC and H3BTC linkers. In contrast to the frequently observed single hexagonal channel type, the acs net within Fe-BQDC-BTC-TPBTC possesses two types of hexagonal channels. One of them is capable of fitting two differently sized C3-symmetry ligands, engendering an unusual quaternary MOF with a new partially partitioned acs 2/3-plus net eventually. Fe-BQDC-BTC-TPBTC demonstrates a complex bimodal porous system concomitant with a potential separation property toward the MTO product of ethylene and propene mixtures as verified by single gas adsorption and transient column breakthrough experiments, respectively.