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During the past decade, research on the design and synthesis of zeolite‐like metal–organic frameworks (ZMOFs) has developed greatly. As an important subclass of ZMOFs, zeolite‐like cluster organic frameworks (ZCOFs) built from 4‐connected metal‐cluster secondary building units (SBUs) and appropriate linear organic ligand bridges have attracted sustained interest, because such materials not only integrate the merits of inorganic zeolites, ZMOFs, and metal clusters, including interesting topologies, high surface areas, extra‐large cavities and channels, structural tunability, and unique physicochemical properties from various metal clusters, but also open up a new avenue to design and fabricate hybrid zeolite‐like materials that have many potential applications in material sciences. In this review, recent developments in ZCOFs are summarized by classifying the ZCOFs into four categories according to the composition of the SBUs: 1) ZCOFs based on metal–halide cluster SBUs, 2) ZCOFs based on metal–oxygen cluster SBUs, 3) ZCOFs based on metal–chalcogen cluster SBUs, and 4) ZCOFs based on mixed types of metal‐cluster SBUs. Besides, challenges associated with the design and synthesis of ZCOFs and the vast potential of this area are also discussed. A frame of reference: Zeolite‐like cluster organic frameworks (ZCOFs) built from 4‐connected metal‐cluster secondary building units (SBUs) have attracted sustained interest due to their charming structures and potential applications in materials sciences. This Minireview presents a summary of recent advances in the development of ZCOF materials. Challenges associated with the design and synthesis of ZCOFs and the vast potential of this area are also discussed. [ABSTRACT FROM AUTHOR]

Two zeolite-like cluster organic frameworks based on Cd-Cu/Mn-Cu heterometallic supertetrahedral secondary building units have been successfully constructed under solvothermal conditions, namely, Cu[Cd4Cu6(L)4(H2O)18](Ac)9 ⋅DMA ⋅3 H2O ( 1), and Cu[Mn4Cu6(L)4(Ac)3(H2O)12](Ac)6 ⋅CH3CN ⋅13 H2O ( 2), where H3L=2-(hydroxymethyl)-2-(pyridin-4-yl)-1,3-propanediol, Ac=CH3COO−, DMA= N, N′-dimethylacetamide. Single-crystal X-ray structural analysis reveals that both 1 and 2 exhibit 3-dimensional zeolite-like architectures with similar 4-connected components, but possess definitely different topologies of diamondoid (dia) and uncommon lonsdaleite (lon), respectively. 1 and 2 represent the first cases of zeolite-like cluster organic frameworks containing Cd-Cu/Mn-Cu heterometallic supertetrahedral secondary building units. Furthermore, the magnetic properties and porous nature of 1 and 2 were also studied. [ABSTRACT FROM AUTHOR]