Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Dushu Lake Campus, Soochow University, Suzhou 215123, People's Republic of China.
Dalton Trans. 2012 Oct 28;41(40):12439-45. doi: 10.1039/c2dt30960b.
Solvothermal reactions of elements Ge and Se with Ln(2)O(3) in a pentadentate polyamine, tetraethylenepentamine (tepa), produced novel neutral lanthanide-selenidogermanate polymers {Ln(tepa)(μ-OH)}(2)(μ-Ge(2)Se(8)) (Ln = Eu 1, Gd 2, Dy 3). The reaction with Dy(2)O(3) in ethylenediamine (en) afforded an ionic selenidogermanate [{Dy(en)(3)}(2)(μ-OH)(2)]Ge(2)Se(6) (4). In compounds 1-3, the Ln(3+) ions are coordinated by a tepa and two OH(-) ligands to form binuclear {Ln(tepa)}(2)(μ-OH)(2) fragments. Two GeSe(4) tetrahedra are linked through two Se-Se bonds to form a novel Ge(2)Se(8) unit containing a six-membered Ge(2)Se(4) ring in the chair conformation. The Ge(2)Se(8) unit acts as a bridging ligand via the trans terminal Se atoms to interlink the {Ln(tepa)}(2)(μ-OH)(2) fragments into one-dimensional polymers {Ln(tepa)(μ-OH)}(2)(μ-Ge(2)Se(8)). Compounds 1-3 are the first examples of solvothermally prepared lanthanide complexes with a selenidogermanate anion as a ligand. The Ge(2)Se(6) anion in 4 is composed of two GeSe(4) tetrahedra sharing a common edge, and is charge compensated by a {Dy(en)(5)}(2)(μ-OH)(2) complex cation. The formation of the Ge(2)Se(8) and Ge(2)Se(6) anions and their behavior towards lanthanide ions in 1-4 show the significant influence of ethylene polyamines on the solvothermal synthesis of Ln selenidogermanates.
元素 Ge 和 Se 与 Ln(2)O(3) 在五齿多胺四乙烯五胺（tepa）中的溶剂热反应生成了新型中性镧系元素硒化锗聚合物{Ln(tepa)(μ-OH)}(2)(μ-Ge(2)Se(8))（Ln = Eu 1，Gd 2，Dy 3）。与 Dy(2)O(3) 在乙二胺（en）中的反应生成了离子型硒化锗盐[{Dy(en)(3)}(2)(μ-OH)(2)]Ge(2)Se(6)（4）。在化合物 1-3 中，Ln(3+)离子由 tepa 和两个 OH(-)配体配位，形成双核{Ln(tepa)}(2)(μ-OH)(2)片段。两个 GeSe(4)四面体通过两个 Se-Se 键连接，形成一个新型Ge(2)Se(8)单元，其中包含一个椅式构象的六元 Ge(2)Se(4)环。Ge(2)Se(8)单元通过反式末端 Se 原子作为桥联配体将{Ln(tepa)}(2)(μ-OH)(2)片段连接成一维聚合物{Ln(tepa)(μ-OH)}(2)(μ-Ge(2)Se(8))。化合物 1-3 是首例溶剂热制备的以硒化锗阴离子为配体的镧系元素配合物。化合物 4 中的Ge(2)Se(6)阴离子由两个共享一个共同边缘的 GeSe(4)四面体组成，由{Dy(en)(5)}(2)(μ-OH)(2)配合阳离子电荷补偿。Ge(2)Se(8)和Ge(2)Se(6)阴离子的形成及其在 1-4 中对镧系元素离子的行为表明，乙烯多胺对镧系元素硒化锗的溶剂热合成有显著影响。
