Tang Shimei, Zhou Jian, Zou Hua-Hong, Liu Xing, Zhang Li
Chongqing Key Laboratory of Inorganic Functional Materials, College of Chemistry, Chongqing Normal University , Chongqing 401331, P. R. China.
State Key Laboratory for Chemistry and Molecular Engineering of Medicinal Resources, School of Chemistry & Pharmacy of Guangxi Normal University , Guilin 541004, P. R. China.
Inorg Chem. 2018 Feb 5;57(3):1242-1250. doi: 10.1021/acs.inorgchem.7b02659. Epub 2018 Jan 10.
A series of lanthanide selenidogermanates, (Hpeha)[Ln(μ-OH)(tepa)Cl]{Ln(μ-OH)(tepa)Cl}[GeSe]Cl [Ln = Y (1a) and Er (1b); peha = pentaethylenexamine, tepa = tetraethylenepentamine], [Sm(μ-OH)(tepa)(μ-GeSe)] (2), [Ho(μ-OH)(tepa)(μ-GeSe)] (3), and [Ce(tepa)(μ-GeSe)(μ-GeSe)(μ-GeSe)] (4), were made under solvothermal conditions. Compounds 1a and 1b contain a protonated Hpeha ion, the complex cation [Ln(μ-OH)(tepa)Cl], a [GeSe] anion, free Cl ions, and a {Ln(μ-OH)(tepa)Cl} cation constructed by two unsaturated [Ln(μ-OH)(tepa)Cl] groups connecting via the trans terminal Se atoms of the [GeSe] anion, which provides the first example of an organic decorated lanthanide selenidogermanate cation. Both compounds 2 and 3 contain one-dimensional chains [Ln(μ-OH)(tepa)(μ-GeSe)] constructed by a combination of unsaturated complex cations [Ln(μ-OH)(tepa)] and [GeSe] anions, but their stacking patterns of neutral chains are different. Compound 4 contains one-dimensional chain [Ce(tepa)(μ-GeSe)(μ-GeSe)(μ-GeSe)], where three different selenidogermanate units acting as bridging ligands connect unsaturated [Ce(tepa)] ions. Compound 4 represents the first example of the coexistence of three different selenidogermanate anions in the same architecture. Their optical properties are studied, and the magnetic properties of compounds 1b and 2-4 are also investigated.
通过溶剂热法合成了一系列镧系硒基锗酸盐，即(Hpeha)[Ln(μ-OH)(tepa)Cl]{Ln(μ-OH)(tepa)Cl}[GeSe]Cl [Ln = Y (1a) 和 Er (1b)；peha = 五乙烯六胺，tepa = 四乙烯五胺]、[Sm(μ-OH)(tepa)(μ-GeSe)] (2)、[Ho(μ-OH)(tepa)(μ-GeSe)] (3) 和 [Ce(tepa)(μ-GeSe)(μ-GeSe)(μ-GeSe)] (4)。化合物1a和1b包含一个质子化的Hpeha离子、络合阳离子[Ln(μ-OH)(tepa)Cl]、一个[GeSe]阴离子、游离的Cl离子，以及一个由两个不饱和[Ln(μ-OH)(tepa)Cl]基团通过[GeSe]阴离子的反式端基Se原子连接而成的{Ln(μ-OH)(tepa)Cl}阳离子，这提供了有机修饰的镧系硒基锗酸盐阳离子的首个实例。化合物2和3均包含由不饱和络合阳离子[Ln(μ-OH)(tepa)]和[GeSe]阴离子组合构建而成的一维链[Ln(μ-OH)(tepa)(μ-GeSe)]，但它们中性链的堆积模式不同。化合物4包含一维链[Ce(tepa)(μ-GeSe)(μ-GeSe)(μ-GeSe)]，其中三个不同的硒基锗酸盐单元作为桥连配体连接不饱和的[Ce(tepa)]离子。化合物4代表了在同一结构中三种不同硒基锗酸盐阴离子共存的首个实例。研究了它们的光学性质，并对化合物1b和2 - 4的磁性进行了研究。
