Synthesis, structures, and magnetic properties of iron(II) complexes, [Fell(HLMe)2](ClO4)2 and its ethanol adduct [Fell(HLMe)2](ClO4)2・EtOH (HLMe=2-methylimidazol-4-yl-methylideneamino-2-ethylpyridine): Their structural distortion and otha・01 adduct spin
Synthesis, structures, and magnetic properties of iron(II) complexes, [Fell(HLMe)2](ClO4)2 and its ethanol adduct [Fell(HLMe)2](ClO4)2・EtOH (HLMe=2-methylimidazol-4-yl-methylideneamino-2-ethylpyridine): Their structural distortion and otha・01 adduct spin
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铁(II)配合物[Fell(HLMe)2](ClO4)2及其乙醇加合物[Fell(HLMe)2](ClO4)2·EtOH (HLMe=2-methylimidazol-4)的合成、结构和磁性-yl-亚甲基氨基-2-乙基吡啶）：它们的结构畸变和otha·01加合物自旋
DOI：
10.1016/j.poly.2012.09.010
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发表时间：
2012
期刊：
影响因子：
2.6
通讯作者：
Hiroaki Hagiwara
中科院分区：
文献类型：
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作者：
Hiroaki Hagiwara
采用选择性结晶法在甲醇和乙醇中分别合成了两个新的铁（II）配合物[FeII(HLMe)2](ClO4)2(1)及其乙醇加合物[FeII(HLMe)2](ClO4)2·乙氧基(2)，其中hlme2为三齿n3配体2-甲基咪唑-4-酰基甲基氨基-2-乙基吡啶，并对其结构和磁性进行了研究。每个化合物含有相同的八面体n6配位络合阳离子[FeII(HLMe)2]2+和两个ClO4−离子。非溶剂化化合物1是在5-300K温度范围内无自旋跃迁的HS （S=2）配合物，具有由ClO4 -离子与相邻的[FeII(HLMe)2]2+阳离子的咪唑NH基团之间的分子间NH···O−氢键构成的同手性一维螺旋链结构。乙醇加合物2在HS （S=2）和LS （S=0）态之间表现出逐步的一步自旋跃迁，具有两个晶体独立的铁（II）位，其中Fe(1)位有两个NH（咪唑）··OH（EtOH）··O（ClO4−）氢键，Fe(2)位有两个NH（咪唑）··O（ClO4−）氢键。在2的晶格中没有进一步的分子间相互作用来产生扩展结构。热自旋跃迁的存在与否与这些高氯酸盐的每个HS分子的结构畸变及其周围的分子间氢键有关。
Two new iron(II) complexes, [FeII(HLMe)2](ClO4)2(1) and its ethanol adduct [FeII(HLMe)2](ClO4)2·EtOH (2) were synthesized by selective crystallization in methanol and ethanol, respectively, where HLMeis a tridentate N3ligand, 2-methylimidazol-4-yl-methylideneamino-2-ethylpyridine, and their structures and magnetic properties were investigated. Each compound contains the same octahedrally N6coordinated complex-cation [FeII(HLMe)2]2+and two ClO4−ions. The non-solvated compound 1 is the HS (S=2) complex without spin transition over the 5–300K temperature range, and has the homochiral 1D helical-chain structure constructed of the intermolecular NH···O−hydrogen bonds between ClO4−ions and neighboring imidazole NH groups of the [FeII(HLMe)2]2+cations. The ethanol adduct 2 shows a gradual one-step spin transition between the HS (S=2) and LS (S=0) states, and has two crystallographically independent iron(II) sites with two NH(imidazole)···OH(EtOH)···O(ClO4−) hydrogen bonds of Fe(1) site and two NH(imidazole)···O(ClO4−) hydrogen bonds of Fe(2) site. There are no further intermolecular interactions to produce an extended structure in a crystal lattice of 2. The presence or absence of thermal spin transition is related to the structural distortion of each HS molecule of these perchlorate salts associated with their surroundings of intermolecular hydrogen bonds.