Direct solvothermal growth, crystal structures, and optical properties of one-dimensional lanthanide selenidoarsenate(v) polymers [Ln(dien)2(micro3-AsSe4)] (Ln = Nd, Sm): the first example of an AsSe4(3-) anion acting as a ligand to a lanthanide complex.
Direct solvothermal growth, crystal structures, and optical properties of one-dimensional lanthanide selenidoarsenate(v) polymers [Ln(dien)2(micro3-AsSe4)] (Ln = Nd, Sm): the first example of an AsSe4(3-) anion acting as a ligand to a lanthanide complex.
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DOI：
10.1039/b701995e
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发表时间：
2007-05
影响因子：
4
通讯作者：
Dingxian Jia;Aimei Zhu;J. Deng;Yong Zhang;J. Dai
中科院分区：
文献类型：
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作者：
Dingxian Jia;Aimei Zhu;J. Deng;Yong Zhang;J. Dai
在溶剂热条件下，以二烯为溶剂，用As（2）O（3）和Se与Nd（2）O（3）或Sm（2）O（3）反应，合成了两种新的稀土硒砷酸盐（v）[Ln（dien）2（micro（3）-AsSe（4））]（Ln = Nd 1，Sm 2，dien =二乙烯三胺）.化合物1和2属于正交晶系，空间群分别为Iba 2和Pbca。[AsSe（4）]（3-）阴离子作为三齿微（3）-AsSe（4）配体桥接镧系元素[Ln（dien）2]（3+）络合物，导致一维中性[Ln（dien）（2）（微（3）-AsSe（4））]（无限）链。分子链之间通过氢键作用形成网络结构。镧系中心位于一个九配位的环境中，包括两个二烯配体的六个N原子和两个不同四面体[AsSe（4）]（3-）阴离子的三个Se原子，形成一个扭曲的单帽正方形反棱柱。新型配位聚合物[Nd（dien）2（micro（3）-AsSe（4））]（infinity）和[Sm（dien）2（micro（3）-AsSe（4））]（infinity）是溶剂热法合成的以[AsSe（4）]（3-）阴离子为配体的硒砷酸盐的第一个例子。从光学吸收光谱中得到了1的带隙为2.11 eV，2的带隙为2.18 eV。TG-DSC曲线表明，两种化合物在一个单一的步骤中去除配位的二烯配体。
Two novel lanthanide selenidoarsenates(v) [Ln(dien)2(micro(3)-AsSe(4))] (Ln = Nd 1, Sm 2, dien = diethylenetriamine) were synthesized by the reactions of As(2)O(3) and Se with Nd(2)O(3) or Sm(2)O(3) in dien under solvothermal conditions. 1 and 2 are in the orthorhombic crystal system with Iba2 and Pbca space groups, respectively. The [AsSe(4)](3-) anion acts as a tridentate micro(3)-AsSe(4) ligand to bridge the lanthanide [Ln(dien)2](3+) complexes leading to one-dimensional neutral [Ln(dien)(2)(micro(3)-AsSe(4))](infinity) chains. The chains contact through hydrogen bonding to form network structures. The lanthanide center lies within a nine-coordinated environment involving six N atoms of two dien ligands and three Se atoms of two different tetrahedral [AsSe(4)](3-) anions forming a distorted monocapped square antiprism. The novel coordination polymers [Nd(dien)2(micro(3)-AsSe(4))](infinity) and [Sm(dien)2(micro(3)-AsSe(4))](infinity) are the first examples of solvothermally synthesized selenidoarsenates with [AsSe(4)](3-) anion acting as a ligand in lanthanide complexes. The band gaps of 2.11 eV for 1, and 2.18 eV for 2 have been derived from optical absorption spectra. TG-DSC curves show that two compounds remove coordinated dien ligands in a single step.