Abstract
AbstractCup‐shaped molecules are of great interest due to their appealing architectures and properties. Compared with widely studied calixarenes, polyoxometalate‐based cup‐shaped molecules currently remain a virgin land waiting for exploration. In this work, we report the first discovery of two giant cup‐shaped inorganic–organic hybrid polyoxoniobates (PONbs) of {Cu12Nb120} and {Cd16Nb128}. The former integrates three tricyclic Nb24clusters and a hexacyclic Nb48cluster into a cup‐shaped molecule via a Cu12metallacalixarene, while the latter unifies two tricyclic Nb24clusters and a brand‐new pentacyclic Nb40cluster into another cup‐shaped molecule via a hybrid Cd16unit. With 132 and 144 metal centers, {Cu12Nb120} and {Cd16Nb128} show the largest two inorganic–organic hybrid PONbs known to date.
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