Giant Polyoxoniobate‐Based Inorganic Molecular Tweezers: Metal Recognitions, Ion‐Exchange Interactions and Mechanism Studies

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 un...

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Published inAngewandte Chemie International Edition Vol. 62; no. 7; pp. e202217926 - n/a
Main Authors Wu, Ping‐Xin, Guo, Zheng‐Wei, Lai, Rong‐Da, Li, Xin‐Xiong, Sun, Cai, Zheng, Shou‐Tian
Format Journal Article
LanguageEnglish
Published Germany Wiley Subscription Services, Inc 06.02.2023
EditionInternational ed. in English
Subjects
Cations
Core-shell structure
Crystals
Indium
Ion-Exchange
Metal ions
Metal Recognitions
Metals
Nanoclusters
Polyoxometalates
Polyoxoniobates
Polyoxoniobates
Polyoxometalates
Metal Recognitions
Ion-Exchange
Nanoclusters
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Summary: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. The twelve {Nb6} units on the surface of a giant polyoxoniobate cluster can function as six pairs of polyoxoniobate‐based inorganic molecular tweezers with unique C2v‐symmetry binding cavities. They exhibit selective metal‐uptake behaviours.
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ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202217926