Giant Hollow Heterometallic Polyoxoniobates with Sodalite‐Type Lanthanide–Tungsten–Oxide Cages: Discrete Nanoclusters and Extended Frameworks

Abstract

The first series of niobium-tungsten-lanthanide (Nb-W-Ln) heterometallic polyoxometalates {Ln₁₂ W₁₂ O₃₆ (H₂ O)₂₄ (Nb₆ O₁₉ )₁₂ } (Ln=Y, La, Sm, Eu, Yb) have been obtained, which are comprised of giant cluster-in-cluster-like ({Ln₁₂ W₁₂ }-in-{Nb₇₂ }) structures built from 12 hexaniobate {Nb₆ O₁₉ } clusters gathered together by a rare 24-nuclearity sodalite-type heterometal-oxide cage {Ln₁₂ W₁₂ O₃₆ (H₂ O)₂₄ }. The Nb-W-Ln clusters present the largest multi-metal polyoxoniobates and a series of rare high-nuclearity 4d-5d-4f multicomponent clusters. Furthermore, the giant Nb-W-Ln clusters may be isolated as discrete inorganic alkali salts and can be used as building blocks to form high-dimensional inorganic-organic hybrid frameworks.