Magnetic Properties of V-substitution Effect an Iron Mixed-Valence Complex
Magnetic Properties of V-substitution Effect an Iron Mixed-Valence Complex
复制标题
V取代对铁混合价络合物磁性的影响
DOI：
10.1016/j.poly.2017.04.006
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发表时间：
2017
期刊：
影响因子：
2.6
通讯作者：
M. Enomoto
中科院分区：
文献类型：
--
作者：
N. Shida;Y. Suzawa;M. Inaba;A. Okazawa;N. Kojima;M. Enomoto
铁的混合价配合物（n-C3 H7）4 N [FeIIFeIII（dto）3]（dto = C2 O2 S2）表现出一种新的相变类型，即FeII和FeIII之间的电子转移，称为电荷转移相变（CTPT）。CTPT的存在高度依赖于Zn、Mn、Cr或Co对（n-C3 H7）4 N [FeIIFeIII（dto）3]中相应Fe位的3d金属取代。在此，我们制备了一系列磁稀释配合物（n-C3 H7）4 N [FeIIFeIII 1 −xVIIIx（dto）3]（x= 0-1），并对其磁性进行了研究。从磁化率测量判断，不存在与其他3d金属替代情况不同的CTPT抑制。此外，57 Fe穆斯堡尔谱表明，在x = 1.00的情况下，约60%的FeII位从高自旋转变为低自旋。由于金属离子（Fe Ⅱ、Fe Ⅲ和VIII）与配体的配位点（dto中的O或S）之间软硬度的差异，这一行为可解释为配合物形成过程中桥连配体的键异构化。
The iron mixed-valence complex (n-C3H7)4N[FeIIFeIII(dto)3] (dto = C2O2S2) exhibits a novel type of phase transition according electron transfer between FeIIand FeIIIcalled charge transfer phase transition (CTPT). The existence of the CTPT highly depends on the 3d metal substitution with Zn, Mn, Cr, or Co for corresponding Fe site in (n-C3H7)4N[FeIIFeIII(dto)3]. Here, we prepared a series of magnetically diluted complexes (n-C3H7)4N[FeIIFeIII1−xVIIIx(dto)3] (x= 0–1), and carried out investigation of magnetic properties. Judging from the magnetic susceptibility measurement, there is no suppression of the CTPT unlike other 3d metal substituted cases. Moreover,57Fe Mössbauer spectroscopy revealed that about 60% of FeIIsites changed their spin states from high spin to low spin in case of substitution rate forx= 1.00. Since the difference of hardness and softness between metallic ions (FeII, FeIIIand VIII) and coordination sites of ligand (O or S in dto), this behavior is explained by the linkage isomerization of bridging ligand in formation process of the complex.