Synthesis, Characterization, and Magnetism of µ‐2‐Chloroterephthalato‐Bridged Binuclear Lanthanide(III) Complexes

Synthesis and Reactivity in Inorganic and Metal-organic Chemistry Pub Date : 2004-05-01 DOI:10.1081/SIM-120037519

Cui‐Wei Yan, Yan-Tuan Li, Chunyuan Zhu

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Abstract

Abstract Nine new binuclear lanthanide(III) complexes described by the overall formula [Ln2(CTPHA)(Me2bpy)4(ClO4)2](ClO4)2 (Ln = Y, La, Nd, Eu, Gd, Tb, Dy, Ho, Er; Me2bpy = 4,4′‐dimethyl‐2,2′‐bipyridine; and CTPHA = 2‐chloroterephthalate dianion), have been synthesized and characterized by elemental analyses, molar conductance measurements, and IR, ESR, and electronic spectra studies. It is proposed that these complexes have CTPHA‐bridged structures consisting of two lanthanide(III) ions. The variable‐temperature magnetic susceptibility (4–300 K) of [Gd2(CTPHA)(Me2bpy)4(ClO4)2](ClO4)2 was further measured and the magnetic analysis was carried out by means of a least‐square method to fit the observed data with the susceptibility equation derived from the spin Hamiltonian operator, Ĥ = −2J Ŝ 1 Ŝ 2, giving the exchange parameter J = −0.12 cm−1. This result indicates that the operation of a very weak antiferromagnetic spin‐exchange interaction between the adjacent gadolinium(III) and gadolinium(III) ions within the complex.

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µ‐2‐氯对苯二甲酸桥联双核镧系(III)配合物的合成、表征和磁性研究

用总式[Ln2(CTPHA)(Me2bpy)4(ClO4)2](ClO4)2 (Ln = Y, La, Nd, Eu, Gd, Tb, Dy, Ho, Er)描述的九种新型双核镧系(III)配合物;Me2bpy = 4,4′‐二甲基‐2,2′‐联吡啶;和CTPHA = 2‐氯对苯二甲酸二钠)，已经合成并通过元素分析，摩尔电导测量，IR, ESR和电子光谱研究进行了表征。提出这些配合物具有由两个镧系(III)离子组成的CTPHA -桥接结构。进一步测量了[Gd2(CTPHA)(Me2bpy)4(ClO4)2](ClO4)2的变温磁化率(4 - 300 K)，并用最小二乘法将观测数据与自旋哈密顿算子推导的磁化率方程Ĥ =−2J Ŝ 1 Ŝ 2拟合，得到交换参数J =−0.12 cm−1。这一结果表明配合物内相邻的钆(III)和钆(III)离子之间存在非常弱的反铁磁自旋交换相互作用。

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Synthesis and Reactivity in Inorganic and Metal-organic Chemistry

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