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基于二乙酸配体的钴(II)片状体系:从细微的结构差异到不同的磁行为。

Cobalt(II) sheet-like systems based on diacetic ligands: from subtle structural variances to different magnetic behaviors.

机构信息

Laboratorio de Rayos X y Materiales Moleculares, Departamento de Física Fundamental II, Facultad de Física, Universidad de La Laguna, Avenida Astrofísico Francisco Sánchez s/n, E-38204 La Laguna, Tenerife, Spain.

出版信息

Inorg Chem. 2009 Jul 6;48(13):6086-95. doi: 10.1021/ic9004483.

Abstract

The preparation, X-ray crystallography, and magnetic investigation of the compounds Co(H(2)O)(2)(phda) (1), Co(phda) (2), and Co(chda) (3) [H(2)phda = 1,4-phenylenediacetic acid and H(2)chda = 1,1-cyclohexanediacetic acid] are described herein. The cobalt atoms in this series are six- (1) and four-coordinated (2 and 3) in distorted octahedral (CoO(6)) and tetrahedral (CoO(4)) environments. The structures of 1-3 consists of rectangular-grids which are built up by sheets of cobalt atoms linked through anti-syn carboxylate bridges, giving rise to either a three-dimensional structure across the phenyl ring (1 and 2) or to regularly stacked layers with the cyclohexyl groups acting as organic separators (3). The magnetic properties of 1-3 were investigated as a function of the temperature and the magnetic field. Ferromagnetic coupling between the six-coordinate cobalt(II) ions across the anti-syn carboxylate bridge occurs in 1 (J = +1.2 cm(-1)) whereas antiferromagnetic coupling among the tetrahedral cobalt(II) centers within the sheets is observed in 2 and 3 [J = -1.63 (2) and -1.70 cm(-1) (3)] together with a spin-canted structure in 3 giving rise a long-range magnetic ordering (T(c) = 7.5 K).

摘要

本文描述了配合物Co(H(2)O)(2)(phda)(1)、Co(phda)(2)和Co(chda)(3)[H(2)phda = 1,4-苯二乙酸和 H(2)chda = 1,1-环己二乙酸]的制备、X 射线晶体学和磁性研究。该系列中的钴原子呈六配位(1)和四配位(2 和 3),分别处于扭曲的八面体(CoO(6))和四面体(CoO(4))环境中。1-3 的结构由通过反式羧酸盐桥连接的钴原子层片构成的矩形网格组成,导致苯环(1 和 2)上的三维结构或环己基作为有机间隔物(3)的规则堆叠层。1-3 的磁性性质作为温度和磁场的函数进行了研究。在 1 中,反式羧酸盐桥连接的六配位钴(II)离子之间发生铁磁耦合(J = +1.2 cm(-1)),而在 2 和 3 中,片内的四面体钴(II)中心之间观察到反铁磁耦合[J = -1.63(2)和-1.70 cm(-1)(3)],同时 3 中存在自旋倾斜结构,导致长程磁有序(T(c) = 7.5 K)。

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