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Updated: Jun 30, 2025
Author Spotlight: Functionalizing Metal-Organic Frameworks: Advancements, Challenges, and the Power of Post-Synthetic Ligand Exchange
Published on: June 23, 2023
Postsynthetic Installation of Lanthanide Cubane Clusters in a 3D Hydrogen-Bonded Framework of IrIII4ZnII4
Supaphorn Thammakan1, Nobuto Yoshinari1, Marie Tsuchikawa1
1Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan.
Abstract:
Immersing single crystals of (Δ)4-K6[Ir4Zn4O(l-cysteinate)12]·nH2O (K6[1]·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]·nH2O (2; Ln = LaIII, CeIII, PrIII, and NdIII) and Ln0.33[Ln4(OH)4(OAc)3(H2O)7][1]·nH2O (3; 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]·nH2O are completely exchanged by the LnIII ions in 2 and 3, retaining the 3D hydrogen-bonded framework that consists of the IrIII4ZnII4 complex anions of [1]6-. While 2 contained the LnIII ions as isolated aqua species, the LnIII ions in 3 existed as cationic cubane clusters of [Ln4(OH)4(OAc)3(H2O)7]5+; these were linked by [1]6- anions through carboxylate groups in a 3D polymeric structure. 3 showed magnetic and photoluminescence properties that are characteristically observed for discrete LnIII species in the solid state.
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