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Mn2+ 和 Dy3+ 离子与弯曲三羧酸构建的配位聚合物:顺磁和弱反铁磁行为。

Coordination polymers of Mn2+ and Dy3+ ions built with a bent tricarboxylate: metamagnetic and weak anti-ferromagnetic behavior.

机构信息

Department of Chemistry, Indian Institute of Technology, Kanpur, India.

出版信息

Dalton Trans. 2012 Mar 14;41(10):2979-85. doi: 10.1039/c2dt11626j. Epub 2012 Jan 25.

Abstract

Two new coordination polymers have been synthesized with Mn(2+) and Dy(3+) ions using a new bent ether-bridged tricarboxylic acid ligand, o-cpiaH(3) (5-(2-carboxy-phenoxy)-isophthalic acid). The ligand readily reacts with a Mn(2+) salt in presence of pyridine (py) under hydrothermal condition to afford a 3D coordination polymer {[Mn(9)(o-cpia)(6)(py)(3)(3H(2)O)]·H(2)O}(n) (1), that contains two types of polymeric chains. One of them is merely carboxylate bridged Mn(2+) where each metal ion shows both penta- and hexa-coordination. The other chain consists of carboxylate-bridging along with terminally bound pyridines providing both penta- and hexa-coordination to each metal ion. When o-cpiaH(3) is treated with Dy(NO(3))(3).xH(2)O under solvothermal condition, it gives rise to an unusual double layer (6,6) connected 2D coordination polymer {[Dy(o-cpia)]}(n)(2), where each metal ion is hexacoordinated. The double layer 2D sheets are stacked to each other in AA··· fashion through strong C-H···π interactions to generate an overall 3D supramolecular architecture. Both the complexes have been characterized by single crystal X-ray diffraction, IR spectroscopy, thermogravimetry and elemental analysis. Variable temperature magnetic susceptibility measurements indicate that 1 exhibits metamagnetic behavior while 2 shows weak antiferromagnetic behavior.

摘要

两种新的配位聚合物已经用 Mn(2+)和 Dy(3+)离子与一种新的弯曲醚桥联三羧酸配体 o-cpiaH(3)(5-(2-羧基-苯氧基)-间苯二甲酸)合成。在吡啶(py)存在下,配体在水热条件下很容易与 Mn(2+)盐反应,得到一个 3D 配位聚合物 {[Mn(9)(o-cpia)(6)(py)(3)(3H(2)O)]·H(2)O}(n)(1),它包含两种类型的聚合物链。其中一种仅仅是由羧酸盐桥接的 Mn(2+),其中每个金属离子都呈现出五配位和六配位。另一种链由羧酸盐桥接,同时末端结合吡啶,为每个金属离子提供五配位和六配位。当 o-cpiaH(3)与 Dy(NO(3))(3).xH(2)O 在溶剂热条件下反应时,会得到一个不寻常的双层(6,6)连接的 2D 配位聚合物 {[Dy(o-cpia)]}(n)(2),其中每个金属离子都是六配位的。双层 2D 片通过强 C-H···π相互作用堆积在一起,以 AA···方式相互堆积,生成整体 3D 超分子结构。两个配合物都通过单晶 X 射线衍射、红外光谱、热重分析和元素分析进行了表征。变温磁化率测量表明 1 表现出变态磁性行为,而 2 表现出弱反铁磁性行为。

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