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铁(III)配合物[Fe(III)(Him)2(hapen)]AsF6(Him =咪唑,H2hapen = N,N'-双(2-羟基乙酰苯亚甲基)乙二胺)的具有热滞现象的突然自旋转变

Abrupt spin transition with thermal hysteresis of iron(III) complex [Fe(III)(Him)2(hapen)]AsF6 (Him = imidazole, H2hapen = N,N'-bis(2-hydroxyacetophenylidene)ethylenediamine).

作者信息

Fujinami Takeshi, Koike Masataka, Matsumoto Naohide, Sunatsuki Yukinari, Okazawa Atsushi, Kojima Norimichi

机构信息

Department of Chemistry, Faculty of Science, Kumamoto University , Kurokami 2-39-1, Kumamoto 860-8555, Japan.

出版信息

Inorg Chem. 2014 Feb 17;53(4):2254-9. doi: 10.1021/ic402947u. Epub 2014 Feb 5.

Abstract

The solvent-free spin crossover iron(III) complex [Fe(III)(Him)2(hapen)]AsF6 (Him = imidazole, H2hapen = N,N'-bis(2-hydroxyacetophenylidene)ethylenediamine), exhibiting thermal hysteresis, was synthesized and characterized. The Fe(III) ion has an octahedral coordination geometry, with N2O2 donor atoms of the planar tetradentate ligand (hapen) and two nitrogen atoms of two imidazoles at the axial positions. One of two imidazoles is hydrogen-bonded to the phenoxo oxygen atom of hapen of the adjacent unit to give a hydrogen-bonded one-dimensional chain, while the other imidazole group is free from hydrogen bonding. The temperature dependencies of the magnetic susceptibilities and Mössbauer spectra revealed an abrupt spin transition between the high-spin (S = 5/2) and low-spin (S = 1/2) states, with thermal hysteresis.

摘要

合成并表征了无溶剂自旋交叉铁(III)配合物[Fe(III)(Him)2(hapen)]AsF6(Him = 咪唑,H2hapen = N,N'-双(2-羟基乙酰苯亚甲基)乙二胺),该配合物表现出热滞现象。Fe(III)离子具有八面体配位几何结构,平面四齿配体(hapen)的N2O2供体原子以及两个咪唑的两个氮原子位于轴向位置。两个咪唑中的一个通过氢键与相邻单元的hapen的苯氧原子相连,形成氢键一维链,而另一个咪唑基团没有氢键作用。磁化率和穆斯堡尔谱的温度依赖性揭示了在高自旋(S = 5/2)和低自旋(S = 1/2)状态之间的突然自旋转变,并伴有热滞现象。

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