Zhou Jian, Zhao Rong-Qing, Yang Tao, Liu Xing, Xiao Hong-Ping, Zou Hua-Hong, Tan Xiao-Feng
College of Chemistry, Chongqing Normal University, Chongqing, 401331, P. R. China.
Dalton Trans. 2015 Apr 28;44(16):7203-12. doi: 10.1039/c4dt03912b.
A series of new lanthanoid thioarsenates [Ln(teta)(μ-η(1):η(2):η(1)-As(III)S3)]n {Ln = Ce (Ia), Pr (Ib), Nd (Ic), and Sm (Id); teta = triethylenetetramine} and [Ln(teta)(en)(μ-η(1):η(1):η(1)-As(V)S4)]n {Ln = La (IIa), Ce (IIb), Pr (IIc), and Nd (IId); en = ethylenediamine} were prepared by the solvothermal reaction of K3AsO3, S, LnCl3 and organic amines and structurally characterized. Compounds Ia–d crystallise in the orthorhombic space group Aba2 and display 1-D neutral chains [Ln(teta)(μ-η(1):η(2):η(1)-As(III)S3)]n, which represent the first examples of 1-D organic hybrid lanthanoid sulfides built up from trigonal-pyramidal As(III)S3 acting as tetradentate bridging ligands to interlink Ln(teta) ions, while compounds IIa–d crystallise in the orthorhombic space group P2(1)2(1)2(1) and consist of other 1-D neutral chains [Ln(teta)(en)(μ-η(1):η(1):η(1)-As(V)S4)]n, which are built up from the linkages of the tetrahedral As(V)S4 ion and the Ln(teta)(en) ion. To learn more about the influence of lanthanide contraction on the formation of lanthanoid thioarsenates, three organic hybrid lanthanoid thioarsenates [Ln(teta)(en)As(V)S4] [Ln = Dy (IIIa), Ho (IIIb), and Tm (IIIc)] with the neutral molecular structure type in the monoclinic centrosymmetric space group P2(1)/c are also presented. Their optical and magnetic properties have been investigated, and density functional theory calculations of Ia and IIa have also been performed.
通过K3AsO3、S、LnCl3与有机胺的溶剂热反应制备了一系列新型镧系硫代砷酸盐[Ln(teta)(μ-η(1):η(2):η(1)-As(III)S3)]n {Ln = Ce (Ia)、Pr (Ib)、Nd (Ic)和Sm (Id)；teta = 三亚乙基四胺}和[Ln(teta)(en)(μ-η(1):η(1):η(1)-As(V)S4)]n {Ln = La (IIa)、Ce (IIb)、Pr (IIc)和Nd (IId)；en = 乙二胺}，并对其进行了结构表征。化合物Ia–d结晶于正交晶系空间群Aba2，呈现出一维中性链[Ln(teta)(μ-η(1):η(2):η(1)-As(III)S3)]n，这是由三角锥型As(III)S3作为四齿桥连配体连接Ln(teta)离子构成的一维有机杂化镧系硫化物的首个实例，而化合物IIa–d结晶于正交晶系空间群P2(1)2(1)2(1)，由其他一维中性链[Ln(teta)(en)(μ-η(1):η(1):η(1)-As(V)S4)]n组成，这些链由四面体As(V)S4离子与Ln(teta)(en)离子连接而成。为了进一步了解镧系收缩对镧系硫代砷酸盐形成的影响，还展示了三种具有单斜中心对称空间群P2(1)/c中中性分子结构类型的有机杂化镧系硫代砷酸盐[Ln(teta)(en)As(V)S4] [Ln = Dy (IIIa)、Ho (IIIb)和Tm (IIIc)]。研究了它们的光学和磁学性质，并且还对Ia和IIa进行了密度泛函理论计算。
