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

The first series of niobium–tungsten–lanthanide (Nb‐W‐Ln) heterometallic polyoxometalates {Ln12W12O36(H2O)24(Nb6O19)12} (Ln=Y, La, Sm, Eu, Yb) have been obtained, which are comprised of giant cluster‐in‐cluster‐like ({Ln12W12}‐in‐{Nb72}) structures built from 12 hexaniobate {Nb6O19} clusters gathered together by a rare 24‐nuclearity sodalite‐type heterometal–oxide cage {Ln12W12O36(H2O)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. Giant heterometallic polyoxoniobates: A family of polyoxometalate‐based frameworks has been made by integrating s, 3d, 4d, 5d, and 4f metals. Multi‐component self‐assembly offers the first series of niobium–tungsten–lanthanide heterometallic polyoxometalates, which are the largest multi‐metal polyoxoniobates and contain rare nanosized hollow sodalite‐type tungsten–lanthanide–oxide cages.