Two series of aluminum-lanthanide-sodium 12-metallacrown-4 compounds have been synthesized and characterized by single-crystal X-ray analysis. For the individual LnNa(ben)4[12-MCAl(III)N(shi)-4] molecules, where LnIII = Eu (1), Gd (2), Tb (3), Dy (4), Ho (5), Er (6), Tm (7), Yb (8), Lu (9), and Y (10), ben− is benzoate, MC is metallacrown, and shi3− is salicylhydroximate, two independent molecules are present in each unit cell. The aluminum(III) ions and shi3− ligands comprise the MC framework, while the LnIII and Na+ ions bind opposite of each other across the central MC cavity. The benzoate anions serve to tether the LnIII ion to the MC framework. When benzoate is replaced with the dicarboxylate anion isophthalate (iph2−), two [12-MCAl(III)N(shi)-4] units are connected to form a dimer of MCs: {LnNa[12-MCAl(III)N(shi)-4]}2(iph)4, where LnIII = Eu (11), Gd (12), Tb (13), Dy (14), Ho (15), Ho (16), Er (17), Yb (18), and Lu (19). As in 1–10, the aluminum(III) ions and shi3− ligands produce the MC frameworks, and one LnIII ion binds to each central MC cavity. However, there are two binding modes for the sodium ions. For 12–15 and 18, the sodium ions bind to the central MC cavity opposite of the LnIII ions as in 1–10. For 11, 16, 17, and 19, the sodium ions bind to the side of the MC framework by bonding to the phenolate and carboxylate oxygen atoms of two shi3− ligands and to the carboxylate oxygen atom of an iph2− ligand. In these structures, the MC cavity is vacant opposite of the LnIII ions. The substitution of isophthalate for benzoate does not significantly alter the [12-MCAl(III)N(shi)-4] framework as the size of the central MC cavity is not significantly different between analogous lanthanide individual and dimer MCs. However, the identity of the central LnIII ion does determine how close the LnIII ion can approach the mean plane of the oxime oxygen atoms (OoxMP) of the MC cavity. As the ion radius of the central LnIII ion decreases, the LnIII ion is able to more closely approach the OoxMP. For the individual MCs 1–10, the EuIII of 1 is the farthest away from the OoxMP (1.55 Å) and this value steadily decreases to 1.44 Å for the LuIII ion of 9. This same trend is true for the dimer MCs as the EuIII ion of 11 is 1.45 Å from the OoxMP and the LuIII ion of 19 is 1.36 Å from the OoxMP. Though the location of the sodium ions in the dimer MCs does influence the LnIII-OoxMP distance as the absence of the sodium ion in the MC cavity allows the LnIII ion to approach the MC cavity even closer. In 15 a sodium ion is opposite the HoIII ion and the HoIII-OoxMP distance is 1.47 Å, while in 16 the sodium ion is bound to the side of the MC and the HoIII-OoxMP distance is 1.40 Å. The complex GdNa[12-MCAl(III)N(shi)-4]}2(iph)4(DMF)2(H2O)8 is a dimer of [12-MC-4] molecules linked by four isophthalate anions.

中文翻译：

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两类铝-镧系元素-钠杂三金属 12-金属冠-4 化合物的合成和晶体结构：金属冠的单个分子和二聚体

合成了两个系列的铝-镧系元素-钠 12-metallacrown-4 化合物，并通过单晶 X 射线分析对其进行了表征。对于单个 LnNa(ben)4[12-MCAl(III)N(shi)-4] 分子，其中 LnIII = Eu (1), Gd (2), Tb (3), Dy (4), Ho (5 )、Er (6)、Tm (7)、Yb (8)、Lu (9) 和 Y (10)，ben− 是苯甲酸酯，MC 是金属冠，而 shi3− 是水杨酸羟肟酸酯，每个中存在两个独立的分子单元格。铝 (III) 离子和 shi3− 配体构成 MC 骨架，而 LnIII 和 Na+ 离子在中央 MC 腔中彼此相反地结合。苯甲酸阴离子用于将 LnIII 离子束缚在 MC 框架上。当苯甲酸盐被二羧酸阴离子间苯二甲酸盐 (iph2−) 取代时，两个 [12-MCAl(III)N(shi)-4] 单元连接形成 MCs 的二聚体：{LnNa[12-MCAl(III)N( shi)-4]}2(iph)4, 其中 LnIII = Eu (11)、Gd (12)、Tb (13)、Dy (14)、Ho (15)、Ho (16)、Er (17)、Yb (18) 和 Lu (19)。在 1-10 中，铝 (III) 离子和 shi3− 配体产生 MC 骨架，一个 LnIII 离子与每个中央 MC 腔结合。然而，钠离子有两种结合模式。对于 12-15 和 18，钠离子与 LnIII 离子相反的中央 MC 腔结合，如 1-10。对于 11、16、17 和 19，钠离子通过与两个 shi3- 配体的酚盐和羧酸盐氧原子以及 iph2- 配体的羧酸盐氧原子结合，从而与 MC 骨架的侧面结合。在这些结构中，MC 空腔与 LnIII 离子相反。间苯二甲酸酯取代苯甲酸酯不会显着改变 [12-MCAl(III)N(shi)-4] 框架，因为中央 MC 腔的大小在类似的镧系元素和二聚体 MC 之间没有显着差异。然而，中心 LnIII 离子的身份确实决定了 LnIII 离子可以接近 MC 腔的肟氧原子 (OoxMP) 的平均平面的距离。随着中心 LnIII 离子的离子半径减小，LnIII 离子能够更接近 OoxMP。对于单个 MC 1-10，1 的 EuIII 离 OoxMP 最远（1.55 Å），对于 9 的 LuIII 离子，该值稳步下降至 1.44 Å。二聚体 MC 与 EuIII 的趋势相同11 的离子与 OoxMP 相距 1.45 Å，而 19 的 LuIII 离子与 OoxMP 相距 1.36 Å。尽管钠离子在二聚体 MC 中的位置确实会影响 LnIII-OoxMP 距离，因为 MC 腔中没有钠离子允许 LnIII 离子更接近 MC 腔。在 15 中，钠离子与 HoIII 离子相反，HoIII-OoxMP 距离为 1.47 Å，而在 16 中钠离子与 MC 的一侧结合，HoIII-OoxMP 距离为 1.40 Å。复合物 GdNa[12-MCAl(III)N(shi)-4]}2(iph)4(DMF)2(H2O)8 是由四个间苯二甲酸阴离子连接的 [12-MC-4] 分子的二聚体。