A series of heterotrimetallic manganese-lanthanide-sodium dimer metallacrowns has been synthesized and characterized by single-crystal X-ray analysis: {LnNa[12-MCMn(III)N(shi)-4]}2(iph)4, where LnIII = La (1), Ce (2), Pr (3), Nd (4), Sm (5), Eu (6), Gd (7), Tb (8), Dy (9), Ho (10), Er (11), Tm (12), Yb (13), Lu (14), and Y (15); MC is metallacrown; shi3− is salicylhydroximate; and iph2− is isophthalate. The manganese(III) ions and shi3− ligands generate the 12-MC-4 framework with one LnIII and Na+ ion bound to each [12-MCMn(III)N(shi)-4] on opposite sides of the central MC cavity. The carboxylate groups of the isophthalate ligands bridge between the central LnIII ion and each ring MnIII ion, and the meta-arrangement of the carboxylate groups joins two LnNa[12-MCMn(III)N(shi)-4] units together to form the dimer through the LnIII ions, which reside on the interior of the molecule. The identity of the central LnIII ion slightly impacts the size the [12-MCMn(III)N(shi)-4] framework. As the crystal radius of the LnIII ion increases from LuIII (1.02 Å) to LaIII (1.19 Å), the 12-MC-4 framework expands to accommodate the larger LnIII ion as the MC cavity increases in size (0.53 Å for LuIII to 0.58 Å for LaIII) and the average cross cavity MnIII-MnIII and oxime oxygen-oxime oxygen distances also increase (MnIII-MnIII distances: 6.48 Å for LuIII to 6.52 Å for LaIII; Ooxime-Ooxime distances: 3.66 Å for LuIII to 3.75 Å for LaIII). In addition, the larger LnIII ions reside further from the MC cavity as indicated by the LnIII-oxime oxygen mean plane (OoxMP) distance. The LnIII-OoxMP distance steadily decreases from LaIII (1.7527(12) Å) to LuIII (1.5575(15) Å). The complex {LaNa[12-MCMn(III)N(shi)-4]}2(iph)4(DMF)6(H2O)2 is a dimer of [12-MC-4] molecules linked by four isophthalate anions

中文翻译：

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一系列锰-镧系元素-钠12-金属冠-4二聚体的合成和晶体结构

合成了一系列异质三金属锰-镧系元素-钠二聚体金属冠，并通过单晶 X 射线分析表征：{LnNa[12-MCMn(III)N(shi)-4]}2(iph)4，其中 LnIII = La (1), Ce (2), Pr (3), Nd (4), Sm (5), Eu (6), Gd (7), Tb (8), Dy (9), Ho (10) 、Er (11)、Tm (12)、Yb (13)、Lu (14) 和 Y (15)；MC 是金属冠；shi3-是水杨酸羟肟酸酯；iph2-是间苯二甲酸酯。锰 (III) 离子和 shi3- 配体生成 12-MC-4 骨架，其中一个 LnIII 和 Na+ 离子结合到中央 MC 腔两侧的每个 [12-MCMn(III)N(shi)-4]。间苯二甲酸酯配体的羧酸根在中心 LnIII 离子和每个环 MnIII 离子之间架桥，羧酸根的间位排列将两个 LnNa[12-MCMn(III)N(shi)-4] 单元连接在一起形成二聚体通过 LnIII 离子，位于分子内部。中心 LnIII 离子的特性会略微影响 [12-MCMn(III)N(shi)-4] 框架的大小。随着 LnIII 离子的晶体半径从 LuIII (1.02 Å) 增加到 LaIII (1.19 Å)，12-MC-4 骨架随着 MC 腔尺寸的增加而扩展以容纳更大的 LnIII 离子（LuIII 的 0.53 Å 到 0.58 Å 为 LaIII），平均交叉腔 MnIII-MnIII 和肟氧-肟氧距离也增加（MnIII-MnIII 距离：LuIII 的 6.48 Å 至 LaIII 的 6.52 Å；肟-肟距离：LuIII 的 3.66 Å 至 3.75 Å） LaIII)。此外，如 LnIII-肟氧平均平面 (OoxMP) 距离所示，较大的 LnIII 离子离 MC 腔更远。LnIII-OoxMP 距离从 LaIII (1.7527(12) Å) 到 LuIII (1.5575(15) Å) 稳步减小。