Thammakan Supaphorn, Yoshinari Nobuto, Tsuchikawa Marie, Rujiwatra Apinpus, Konno Takumi
Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan.
Department of Chemistry, Faculty of Science, Chiang Mai University, Chiang Mai 50200, Thailand.
Inorg Chem. 2024 Apr 8;63(14):6239-6247. doi: 10.1021/acs.inorgchem.3c04513. Epub 2024 Mar 23.
Immersing single crystals of (Δ)-K[IrZnO(l-cysteinate)]·HO (K[]·HO) bearing 12 free carboxylate groups, which was newly prepared from Δ-H[Ir(l-cysteinate)], ZnBr, ZnO, and KOH, in an aqueous solution of lanthanide(III) acetate produced Ln[]·HO (; Ln = La, Ce, Pr, and Nd) and Ln[Ln(OH)(OAc)(HO)][]·HO (; Ln = Sm, Eu, Gd, Tb, Dy, Er, Ho, Tm, Yb, and Lu) in a single-crystal-to-single-crystal transformation manner. X-ray crystallography showed that the K ions in K[]·HO are completely exchanged by the Ln ions in and , retaining the 3D hydrogen-bonded framework that consists of the IrZn complex anions of []. While contained the Ln ions as isolated aqua species, the Ln ions in existed as cationic cubane clusters of [Ln(OH)(OAc)(HO)]; these were linked by [] anions through carboxylate groups in a 3D polymeric structure. showed magnetic and photoluminescence properties that are characteristically observed for discrete Ln species in the solid state.
将由Δ-H[Ir(半胱氨酸盐)]、ZnBr、ZnO和KOH新制备的带有12个游离羧酸根基团的(Δ)-K[IrZnO(半胱氨酸盐)]·H₂O (K[ ]·H₂O)单晶浸入乙酸镧(III)水溶液中，以单晶到单晶的转变方式生成Ln[ ]·H₂O ( ; Ln = La、Ce、Pr和Nd)以及Ln[Ln(OH)(OAc)(H₂O)][ ]·H₂O ( ; Ln = Sm、Eu、Gd、Tb、Dy、Er、Ho、Tm、Yb和Lu)。X射线晶体学表明，K[ ]·H₂O中的K⁺离子被 和 中的Ln离子完全交换，保留了由[ ]的IrZn络合阴离子组成的三维氢键框架。虽然 中的Ln离子以孤立的水合物种形式存在，但 中的Ln离子以[Ln(OH)(OAc)(H₂O)]的阳离子立方烷簇形式存在；这些通过[ ]阴离子在三维聚合物结构中通过羧酸根基团相连。 表现出固态离散Ln物种特有的磁性和光致发光性质。
