Two Giant<i>Calixarene‐Like</i>Polyoxoniobate Nanocups {Cu<sub>12</sub>Nb<sub>120</sub>} and {Cd<sub>16</sub>Nb<sub>128</sub>} Built from Mixed Macrocyclic Cluster Motifs
Zeng‐Kui Zhu, Jing Zhang, Y. Cong, Rui Ge, Zhong Li, Xin‐Xiong Li, Shou‐Tian Zheng
Abstract
Abstract Cup‐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 {Cu 12 Nb 120 } and {Cd 16 Nb 128 }. The former integrates three tricyclic Nb 24 clusters and a hexacyclic Nb 48 cluster into a cup‐shaped molecule via a Cu 12 metallacalixarene, while the latter unifies two tricyclic Nb 24 clusters and a brand‐new pentacyclic Nb 40 cluster into another cup‐shaped molecule via a hybrid Cd 16 unit. With 132 and 144 metal centers, {Cu 12 Nb 120 } and {Cd 16 Nb 128 } show the largest two inorganic–organic hybrid PONbs known to date.