Postsynthetic Installation of Lanthanide Cubane Clusters in a 3D Hydrogen-Bonded Framework of Ir III 4 Zn II 4 Multicarboxylates.

Immersing single crystals of (Δ)4 -K6 [Ir4 Zn4 O(l-cysteinate)12 ]· n H2 O (K6 [ 1 Ir ]· n H2 O) bearing 12 free carboxylate groups, which was newly prepared from Δ-H3 [Ir(l-cysteinate)3 ], ZnBr2 , ZnO, and KOH, in an aqueous solution of lanthanide(III) acetate produced Ln2 [ 1 Ir ]· n H2 O ( 2 Ln ; Ln = LaIII , CeIII , PrIII , and NdIII ) and Ln0.33 [Ln4 (OH)4 (OAc)3 (H2 O)7 ][ 1 Ir ]· n H2 O ( 3 Ln ; Ln = SmIII , EuIII , GdIII , TbIII , DyIII , ErIII , HoIII , TmIII , YbIII , and LuIII ) in a single-crystal-to-single-crystal transformation manner. X-ray crystallography showed that the KI ions in K6 [ 1 Ir ]· n H2 O are completely exchanged by the LnIII ions in 2 Ln and 3 Ln , retaining the 3D hydrogen-bonded framework that consists of the IrIII 4 ZnII 4 complex anions of [ 1 Ir ]6- . While 2 Ln contained the LnIII ions as isolated aqua species, the LnIII ions in 3 Ln existed as cationic cubane clusters of [Ln4 (OH)4 (OAc)3 (H2 O)7 ]5+ ; these were linked by [ 1 Ir ]6- anions through carboxylate groups in a 3D polymeric structure. 3 Ln showed magnetic and photoluminescence properties that are characteristically observed for discrete LnIII species in the solid state.