Two Giant<i>Calixarene‐Like</i>Polyoxoniobate Nanocups {Cu₁₂Nb₁₂₀} and {Cd₁₆Nb₁₂₈} Built from Mixed Macrocyclic Cluster Motifs

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 {Cu₁₂ Nb₁₂₀ } and {Cd₁₆ Nb₁₂₈ }. The former integrates three tricyclic Nb₂₄ clusters and a hexacyclic Nb₄₈ cluster into a cup-shaped molecule via a Cu₁₂ metallacalixarene, while the latter unifies two tricyclic Nb₂₄ clusters and a brand-new pentacyclic Nb₄₀ cluster into another cup-shaped molecule via a hybrid Cd₁₆ unit. With 132 and 144 metal centers, {Cu₁₂ Nb₁₂₀ } and {Cd₁₆ Nb₁₂₈ } show the largest two inorganic-organic hybrid PONbs known to date.