新型[2 × 2]栅格四核Fe(II)和Ni(II)配合物1,5 -二(1-(吡啶-2-酰基)乙基)羰基肼的合成、晶体结构测定和磁性研究

B. Traoré, T. Seck, M. L. Sall, Antoine Blaise Kama, O. Diouf, I. Thiam, M. Gaye
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摘要

镍(II)和铁(III)的配合物很容易用对称配体1,5-二(1-(吡啶-2-基)乙基)羰基肼(H2L)和金属硝酸盐合成。分离出一个四核铁配合物和一个四核镍配合物的方形[2x2]网格结构。X射线衍射分析表明,两种配合物的晶体结构相似。每个配合物的不对称单元由四个阳离子配体分子和四个金属离子组成。每个配体通过五个配位位点,如两个吡啶氮原子、两个亚甲基氮原子和一个氧原子,以单去质子形式起作用。四个配体分子中的每一个都充当两个金属离子之间的桥梁,产生2 × 2的方形网格结构。每个金属离子都是六配位的,位于N4O2核心中,环境最好描述为严重扭曲的方形双金字塔几何。电化学研究表明,配合物1有两个电子过程,配合物2有一个电子过程。变温磁研究表明,镍(II)中的反铁磁耦合比铁(II)配合物中的强。在这两种配合物中,磁性能与晶体学数据完全相关。
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Synthesis, Crystal Structure Determination and Magnetic Study of a New [2 × 2] Grid Tetranuclear Fe(II) and Ni(II) Complexes Derived from the Ligand 1, 5-Bis(1-(Pyridin-2-Yl) Ethylidene) Carbonohydrazide)
Complexes of nickel (II) and iron (III) are easily synthetized using the symmetrical ligand 1,5-bis(1-(pyridin-2-yl)ethylidene)carbonohydrazide) (H2L) and metal nitrate salts. Square [2x2] grids structure of one tetranuclear iron and one tetranuclear nickel complex were isolated. X ray diffraction analysis reveals that the crystal structures of the two complexes are similar. The asymmetric unit of each complex consists of four cationic ligand molecules and four metal ions. Each ligand acts in its monodeprotonated form through five coordination sites such as two pyridine nitrogen atoms, two azomethine nitrogen atoms and one oxygen atom. Each of the four ligand molecules acts as a bridge between two metal ions yielding a square 2 x 2 grid structure. Each of the metal ion is hexacoordinated and is situated in a N4O2 core and the environment is best described as a severely distorted square bipyramidal geometry. Electrochemical studies show two electrons process for complex 1 and one electron process for complex 2. Variable temperature magnetic study shows that antiferromagnetic coupling is stronger in the nickel(II) than in the iron(II) complex. Perfect correlation between the magnetic properties and the crystallographic data are observed in both complexes.
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