Polynuclear Rare-Earth Cluster-Directed Self-Assembly of Highly Porous Zeolite-like Metal–Organic Frameworks with Methane Storage Property

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.