Postsynthetic Installation of Lanthanide Cubane Clusters in a 3D Hydrogen-Bonded Framework of IrIII4ZnII4 Multicarboxylates

Supaphorn Thammakan; Nobuto Yoshinari; Marie Tsuchikawa; Apinpus Rujiwatra; Takumi Konno

doi:10.1021/acs.inorgchem.3c04513

Postsynthetic Installation of Lanthanide Cubane Clusters in a 3D Hydrogen-Bonded Framework of Ir^III₄Zn^II₄ Multicarboxylates

Inorg Chem. 2024 Apr 8;63(14):6239-6247. doi: 10.1021/acs.inorgchem.3c04513. Epub 2024 Mar 23.

Authors

Supaphorn Thammakan¹, Nobuto Yoshinari¹, Marie Tsuchikawa¹, Apinpus Rujiwatra^{2

3}, Takumi Konno^{1

4}

Affiliations

¹ Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan.
² Department of Chemistry, Faculty of Science, Chiang Mai University, Chiang Mai 50200, Thailand.
³ Materials Science Research Center, Faculty of Science, Chiang Mai University, 239 Huay Kaew Road, Chiang Mai 50200, Thailand.
⁴ Department of Chemistry, College of Science, National Taiwan Normal University, Taipei 11677, Taiwan.

PMID: 38520341
DOI: 10.1021/acs.inorgchem.3c04513

Abstract

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 = La^III, Ce^III, Pr^III, and Nd^III) and Ln_0.33[Ln₄(OH)₄(OAc)₃(H₂O)₇][1^Ir]·nH₂O (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 K₆[1^Ir]·nH₂O 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^III₄Zn^II₄ 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 [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 Ln^III species in the solid state.