Syntheses, three types of hydrogen-bonded assembly structures, and magnetic properties of [Fe^<III>(Him)_2 (hapen)]Y-solvent (Him=imidazole, hapen=N, N-bis (2-hydroxyacetophenylidene) ethylenediamine, y=BPh_4- CF_3 SO_3- PF_6- CIO_4-, and BF_4)
Syntheses, three types of hydrogen-bonded assembly structures, and magnetic properties of [Fe^<III>(Him)_2 (hapen)]Y-solvent (Him=imidazole, hapen=N, N-bis (2-hydroxyacetophenylidene) ethylenediamine, y=BPh_4- CF_3 SO_3- PF_6- CIO_4-, and BF_4)
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[Fe^<III>(Him)_2(hapen)]Y-溶剂(Him=咪唑, hapen=N, N-双(2-羟基乙酰亚苯基)乙二胺的合成、三种氢键组装结构及磁性能
DOI：
10.1016/j.ica.2013.01.021
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发表时间：
2013
影响因子：
2.8
通讯作者：
Yukinari Sunatsuki
中科院分区：
文献类型：
--
作者：
Masataka Koike;Keishiro Murakami;Takeshi Fujinami;Koshiro Nishi;Naohide Matsumoto;Yukinari Sunatsuki
合成了[FeIII(Him)2(hapen)]Y·溶剂与五种不同抗衡阴离子的五种铁(III)络合物，其中Him=咪唑，H2hapen=N,N'-双(2-羟基乙酰亚苯基)乙二胺，Y=BPh4−(1)、CF3SO3−(2)、PF6−(3)、ClO4−(4)和BF4−(5)，溶剂=甲醇或水。每个 FeIIIion 具有八面体配位几何结构，其中赤道四齿配体 (hapen) 的 N2O2 供体原子和两个咪唑的两个氮原子位于轴向位置。咪唑基团与相邻单元的苯氧氧原子和/或抗衡阴离子或溶剂分子通过氢键键合，得到三种类型的组装结构，包括线性二聚体、环状二聚体和一维锯齿形链。化合物 1 具有环状二聚体，化合物 2 和 3 具有一维链，显示出高自旋 (S=5/2) 和低自旋 (S=1/2) 状态之间的自旋平衡行为，而具有线性二聚体的 4 和 5 是高自旋配合物。化合物 3 显示出具有较小热滞后的突然自旋跃迁。
Five iron(III) complexes of [FeIII(Him)2(hapen)]Y·solvent with five different counter anions were synthesized, where Him=imidazole, H2hapen=N,N′-bis(2-hydroxyacetophenylidene)ethylenediamine, Y=BPh4−(1), CF3SO3−(2), PF6−(3), ClO4−(4), and BF4−(5), and solvent=methanol or H2O. Each FeIIIion has octahedral coordination geometry with N2O2donor atoms of the equatorial tetradentate ligand (hapen) and two nitrogen atoms of two imidazoles at the axial positions. The imidazole group is hydrogen-bonded to the phenoxo oxygen atom of hapen of the adjacent unit and/or to the counter anion or solvent molecule, to give three types of assembly structures involving linear dimer, cyclic dimer, and one-dimensional zigzag chain. Compound 1, with a cyclic dimer, and 2 and 3, with a one-dimensional chain, showed spin-equilibrium behavior between high-spin (S=5/2) and low-spin (S=1/2) states, whereas 4 and 5, with linear dimers, are high-spin complexes. Compound 3 shows abrupt spin transition with small thermal hysteresis.