Synthesis, Characterization, and Magnetic Properties of Tetracarboxylato‐Bridged Binuclear Iron(II) Complexes

Cui‐Wei Yan, Yan-Tuan Li, J.-F. Lou, Chunyuan Zhu
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引用次数: 7

Abstract

Abstract Four new binuclear iron(II) complexes with a tetracarboxylato‐bridge have been synthesized and characterized, namely [Fe2(PMTA)L4], where L denotes 4,7‐diphenyl‐1,10‐phenanthroline (Ph2‐phen); 2,9‐dimethyl‐1,10‐phenanthroline (Me2phen); diaminoethane (en); 1,3‐diaminopropane (pn) and PMTA represents the tetraanion of pyromellitic acid. Based on elemental analyses, magnetic moments at room‐temperature and molar conductivity measurements, spectroscopic (electronic and IR spectra) studies, it is proposed that these complexes have PMTA‐bridged structures and consist of two iron(II) ions in a distorted octahedral environment. The variable‐temperature magnetic susceptibilities (4–300 K) of the complexes [Fe2(PMTA)(Ph2phen)4] (1) and [Fe2(PMTA)(Me2phen)4] (2) were measured and studied in detail. The magnetic analysis was carried out by means of a least‐square method to the observed data with the susceptibility equation derived from the spin Hamiltonian operator, Ĥ = −2JŜ 1 Ŝ 2, giving the exchange integrals J = −0.96 cm−1 for (1) and J = −0.85 cm−1 for (2). The results indicate that there is a very weak antiferromagnetic spin‐exchange interaction between the two Fe(II) ions within each molecule.
四羧基桥接双核铁(II)配合物的合成、表征和磁性研究
摘要合成并表征了四羧基桥接的新型双核铁(II)配合物[Fe2(PMTA)L4],其中L表示4,7‐二苯基‐1,10‐菲罗啉(Ph2‐phen);2、9必经地理二甲基1、10邻二氮杂菲(Me2phen);diaminoethane (en);1,3 -二氨基丙烷(pn)和PMTA代表焦二甲基酸的四阴离子。基于元素分析、室温下的磁矩、摩尔电导率测量、光谱(电子和红外光谱)研究,提出这些配合物具有PMTA桥接结构,并且在扭曲的八面体环境中由两个铁(II)离子组成。对配合物[Fe2(PMTA)(Ph2phen)4](1)和[Fe2(PMTA)(Me2phen)4](2)的变温磁化率(4 - 300 K)进行了测量和详细研究。利用自旋哈密顿算子Ĥ =−2JŜ 1 Ŝ 2推导的磁化率方程,利用最小二乘法对观测数据进行了磁性分析,得到(1)的交换积分J =−0.96 cm−1,(2)的交换积分J =−0.85 cm−1。结果表明,每个分子内两个Fe(II)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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