Postsynthetic Installation of Lanthanide Cubane Clusters in a 3D Hydrogen-Bonded Framework of IrZn Multicarboxylates.

Immersing single crystals of (Δ)-K[IrZnO(l-cysteinate)]·HO (K[]·HO) bearing 12 free carboxylate groups, which was newly prepared from Δ-H[Ir(l-cysteinate)], ZnBr, ZnO, and KOH, in an aqueous solution of lanthanide(III) acetate produced Ln[]·HO (; Ln = La, Ce, Pr, and Nd) and Ln[Ln(OH)(OAc)(HO)][]·HO (; Ln = Sm, Eu, Gd, Tb, Dy, Er, Ho, Tm, Yb, and Lu) in a single-crystal-to-single-crystal transformation manner. X-ray crystallography showed that the K ions in K[]·HO are completely exchanged by the Ln ions in and , retaining the 3D hydrogen-bonded framework that consists of the IrZn complex anions of []. While contained the Ln ions as isolated aqua species, the Ln ions in existed as cationic cubane clusters of [Ln(OH)(OAc)(HO)]; these were linked by [] anions through carboxylate groups in a 3D polymeric structure. showed magnetic and photoluminescence properties that are characteristically observed for discrete Ln species in the solid state.