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 -K 6 [Ir 4 Zn 4 O(l-cysteinate) 12 ]· n H 2 O (K 6 [ 1 Ir ]· n H 2 O) bearing 12 free carboxylate groups, which was newly prepared from Δ-H 3 [Ir(l-cysteinate) 3 ], ZnBr 2 , ZnO, and KOH, in an aqueous solution of lanthanide(III) acetate produced Ln 2 [ 1 Ir ]· n H 2 O ( 2 Ln ; Ln = La III , Ce III , Pr III , and Nd III ) and Ln 0.33 [Ln 4 (OH) 4 (OAc) 3 (H 2 O) 7 ][ 1 Ir ]· n H 2 O ( 3 Ln ; Ln = Sm III , Eu III , Gd III , Tb III , Dy III , Er III , Ho III , Tm III , Yb III , and Lu III ) in a single-crystal-to-single-crystal transformation manner. X-ray crystallography showed that the K I ions in K 6 [ 1 Ir ]· n H 2 O are completely exchanged by the Ln III ions in 2 Ln and 3 Ln , retaining the 3D hydrogen-bonded framework that consists of the Ir III 4 Zn II 4 complex anions of [ 1 Ir ] 6- . While 2 Ln contained the Ln III ions as isolated aqua species, the Ln III ions in 3 Ln existed as cationic cubane clusters of [Ln 4 (OH) 4 (OAc) 3 (H 2 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 Ln III species in the solid state.