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This work reports the interesting and unique cation‐exchange behaviors of the first indium‐bridged purely inorganic 3D framework based on high‐nuclearity polyoxoniobates as building units. Each nanoscale polyoxoniobate features a fascinating near‐icosahedral core–shell structure with six pairs of unique inorganic "molecular tweezers" that have changeable openings for binding different metal cations via ion‐exchanges and exhibit unusual selective metal‐uptake behaviors. Further, the material has high chemical stability so that can undergo single‐crystal‐to‐single‐crystal metal‐exchange processes to produce a dozen new crystals with high crystallinity. Based on these crystals and time‐dependent metal‐exchange experiments, we can visually reveal the detailed metal‐exchange interactions and mechanisms of the material at the atomic precision level. This work demonstrates a rare systematic and atomic‐level study on the ion‐exchange properties of nanoclusters, which is of significance for the exploration of cluster‐based ion‐exchange materials that are still to be developed. [ABSTRACT FROM AUTHOR]

Herein, a giant Sb‐rich polyoxometalate (POM) {Sb21Tb7W56} is reported, which contains the largest number of Sb atoms in a POM so far. The Sb‐rich POM has many interesting structural features and is a rare example of a soluble and water‐stable giant POM. Biomedical studies indicate that the Sb‐rich POM exhibits broad‐spectrum antitumor activity against various cancer cell lines by reactivating the P53‐dependent apoptotic processes and disrupting the mitochondrial membrane. In addition, this Sb‐rich POM was capable of suppressing the growth and metastasis of a breast cancer in vivo. This work demonstrates that Sb‐rich POMs are promising candidates for the development of new anticancer drugs. [ABSTRACT FROM AUTHOR]

• The recent advancements of all-inorganic POM cages, including their assembly methodologies, classification and related applications are summarized. • The advantages of using POM clusters as SBUs to construct all-inorganic POM cages are summarized. • Feasible synthetic strategies for further development of all-inorganic POM cages are presented. • Understanding the structure–property/application relationships of all-inorganic POM cages. • The current challenges in the design and fabrication of all-inorganic POM cages as well as the great potential in this area are discussed. Searching for suitable methods to construct all-inorganic cage materials by using polyoxometalates (POMs) as secondary building units (SBUs) has been of great interest, because such materials not only exhibit fascinating cage-shaped structures and unique physicochemical properties derived from both cage architectures and POM clusters, but also have promising and practical applications in areas of molecule separation, guest recognition, molecular reactors, photocatalysis, environmental protection, and so on. In this review, the recent development in all-inorganic POM-based cage materials is summarized, including their assembly methods, structures, properties, and related applications. Moreover, the current challenges in the design and assembly of all-inorganic POM cages as well as the development potential of this area also discussed. [ABSTRACT FROM AUTHOR]

[Display omitted] • The developments of all-inorganic POM-based frameworks including their syntheses, structures, properties and related applications are summarized. • The structure–property/application relationships of all-inorganic POM-based frameworks are summarized. • Feasible synthetic strategies for further development of all-inorganic POM-based frameworks are presented. • The development prospects and the current challenges for all-inorganic POM-based frameworks are discussed. Polyoxometalates (POMs) are an intriguing class of compounds that have been extensively studied due to their unique structures and diverse properties. In the past years, the synthesis of POM-based all-inorganic open frameworks has attracted increasing attention due to their potential applications in various fields, such as in electrode, magnetic, and catalytic materials. This review not only provides a comprehensive survey on POM-based all-inorganic open frameworks, including their structures, properties, and potential applications, but also discusses the current challenges in this field and provides an outlook for future research directions. [ABSTRACT FROM AUTHOR]