Postsynthetic Installation of Lanthanide Cubane Clusters in a 3D Hydrogen-Bonded Framework of IrIII 4ZnII 4 Multicarboxylates

• Published in: Inorganic chemistry 2024-04, Vol.63 (14), p.6239-6247
• Main Authors: Thammakan, Supaphorn, Yoshinari, Nobuto, Tsuchikawa, Marie, Rujiwatra, Apinpus, Konno, Takumi
• Format: Article
• Language: English
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/acs.inorgchem.3c04513

Immersing single crystals of (Δ)4-K6[Ir4Zn4O­(l-cysteinate)12]·nH2O (K6[1 Ir ]·nH2O) 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 ]·nH2O (2 Ln ; Ln = LaIII, CeIII, PrIII, and NdIII) and Ln0.33[Ln4(OH)4(OAc)3(H2O)7]­[1 Ir ]·nH2O (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 ]·nH2O are completely exchanged by the LnIII ions in 2 Ln and 3 Ln , retaining the 3D hydrogen-bonded framework that consists of the IrIII 4ZnII 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(H2O)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.