Record High-Nuclearity Polyoxoniobates: Discrete Nanoclusters {Nb114}, {Nb81}, and {Nb52}, and Extended Frameworks Based on {Cu3Nb78} and {Cu4Nb78}.

A series containing the highest nuclearity polyoxoniobate (PONb) nanoclusters, ranging from dimers to tetramers, has been obtained. They include one 114-nuclear {Li₈⊂Nb₁₁₄O₃₁₆}, one 81-nuclear {Li₃K⊂Nb₈₁O₂₂₅}, and one 52-nuclear {H₄Nb₅₂O₁₅₀}. The Nb nuclearity of these PONbs is remarkably larger than those of all known high-nuclearity PONbs (≤32). Furthermore, the introduction of 3d Cu²⁺ ions can lead to the generation of extended inorganic-organic hybrid frameworks built from novel, high-nuclearity, nanoscale heterometallic PONb building blocks {H₃Cu₃Nb₇₈O₂₂₂} or {H₃Cu₄(en)Nb₇₈O₂₂₂}. These building blocks also contain the largest number of Nb centers of any heterometallic PONbs reported to date. The synthesis of new-type PONbs has long been a challenging subject in PONb chemistry. [ABSTRACT FROM AUTHOR]