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基于氨基酸的 MOFs:钴和镍氨基异酞配合物的合成、结构、单晶到单晶转变、磁性及相关研究。

Amino acid based MOFs: synthesis, structure, single crystal to single crystal transformation, magnetic and related studies in a family of cobalt and nickel aminoisophthales.

机构信息

Framework Solids Laboratory, Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore-560012, India.

出版信息

Inorg Chem. 2009 Dec 21;48(24):11660-76. doi: 10.1021/ic901678c.

DOI:10.1021/ic901678c
PMID:19938871
Abstract

Four new 5-aminoisophthalates of cobalt and nickel have been prepared employing hydro/solvothermal methods: [Co(2)(C(8)H(5)NO(4))(2)(C(4)H(4)N(2))(H(2)O)(2)].3H(2)O (I), [Ni(2)(C(8)H(5)NO(4))(2)(C(4)H(4)N(2))(H(2)O)(2)].3H(2)O (II), [Co(2)(H(2)O)(mu(3)-OH)(2)(C(8)H(5)NO(4))] (III), and [Ni(2)(H(2)O)(mu(3)-OH)(2)(C(8)H(5)NO(4))] (IV). Compounds I and II are isostructural, having anion-deficient CdCl(2) related layers bridged by a pyrazine ligand, giving rise to a bilayer arrangement. Compounds III and IV have one-dimensional M-O(H)-M chains connected by the 5-aminoisophthalate units forming a three-dimensional structure. The coordinated as well as the lattice water molecules of I and II could be removed and inserted by simple heating-cooling cycles under the atmospheric conditions. The removal of the coordinated water molecule is accompanied by changes in the coordination environment around the M(2+) (M = Co, Ni) and color of the samples (purple to blue, Co; green to dark yellow, Ni). This change has been examined by a variety of techniques that include in situ single crystal to single crystal transformation studies and in situ IR and UV-vis spectroscopic studies. Magnetic studies indicate antiferromagnetic behavior in I and II, a field-induced magnetism in III, and a canted antiferromagnetic behavior in IV.

摘要

四种新的钴和镍的 5-氨基异酞酸盐已通过水/溶剂热方法制备:[Co(2)(C(8)H(5)NO(4))(2)(C(4)H(4)N(2))(H(2)O)(2)].3H(2)O (I),[Ni(2)(C(8)H(5)NO(4))(2)(C(4)H(4)N(2))(H(2)O)(2)].3H(2)O (II),[Co(2)(H(2)O)(mu(3)-OH)(2)(C(8)H(5)NO(4))] (III),和[Ni(2)(H(2)O)(mu(3)-OH)(2)(C(8)H(5)NO(4))] (IV)。化合物 I 和 II 是同构的,具有阴离子缺陷的 CdCl(2)相关层,由吡嗪配体桥接,形成双层排列。化合物 III 和 IV 具有一维 M-O(H)-M 链,通过 5-氨基异酞酸盐单元连接,形成三维结构。I 和 II 的配位和晶格水分子可以通过在大气条件下简单的加热-冷却循环去除和插入。配位水分子的去除伴随着 M(2+)(M = Co,Ni)周围的配位环境和样品颜色的变化(紫色到蓝色,Co;绿色到深黄色,Ni)。这种变化已经通过各种技术进行了研究,包括原位单晶到单晶的转化研究以及原位红外和紫外可见光谱研究。磁性研究表明 I 和 II 中存在反铁磁行为,III 中存在场诱导磁性,IV 中存在倾斜反铁磁行为。

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