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手性自旋转换铁(Ⅱ)席夫碱配合物的合成、结构及其磁性研究

任冬红 ,  刘志明 ,  孙晓利 ,  顾玲 ,  邱丹 ,  顾志国 ,  李在均

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引用本文: 任冬红, 刘志明, 孙晓利, 顾玲, 邱丹, 顾志国, 李在均. 手性自旋转换铁(Ⅱ)席夫碱配合物的合成、结构及其磁性研究[J]. 无机化学学报, 2015, (3): 536-542. doi: 10.11862/CJIC.2015.040 shu
Citation:  REN Dong-Hong, LIU Zhi-Ming, SUN Xiao-Li, GU Ling, QIU Dan, GU Zhi-Guo, LI Zai-Jun. Syntheses, Structures and Magnetic Properties of Homochiral Spin-Crossover Iron(Ⅱ) Schiff-Base Complexes[J]. Chinese Journal of Inorganic Chemistry, 2015, (3): 536-542. doi: 10.11862/CJIC.2015.040 shu

手性自旋转换铁(Ⅱ)席夫碱配合物的合成、结构及其磁性研究

  • 1.

    1 江南大学化学与材料工程学院, 无锡 214122;

  • 2.

    2 食品胶体与生物技术教育部重点实验室, 无锡 214122

    • 通讯作者: 顾志国 zhiguogu@jiangnan.edu.cn
  • 基金项目:

    国家自然科学基金(No.21101078, 21276105) (No.21101078, 21276105)

    新世纪优秀人才计划(No.NCET-11-0657) (No.NCET-11-0657)

    江苏省自然科学基金(No.BK2011143)资助。 (No.BK2011143)

摘要: 通过高氯酸亚铁, 4-(咪唑-2-甲醛)丁腈和光学纯苯乙胺衍生物的自组装成功合成了2个纯手性单核自旋转换铁(Ⅱ)化合物fac-Λ-[Fe(R-L1)3](ClO4)2(1), fac-Λ-[Fe(R-L2)3](ClO4)2(2)。利用X-射线单晶衍射、元素分析(EA)、红外光谱(IR)、核磁共振氢谱(1H NMR)、紫外光谱(UV)、圆二光谱(CD)等手段对配合物结构进行了表征。X-射线单晶衍射表明在化合物1和2中, 铁(Ⅱ)金属中心与3个不对称双齿手性席夫碱配体中的6个氮原子配位形成八面体配位环境。每个结构基元中包含1个[Fe(L)3]2+阳离子和2个高氯酸根阴离子。由于铁(Ⅱ)中心周围手性配体的螺旋协调配位使[Fe(L)3]2+形成单一手性Λ构型。Fe(Ⅱ)-N键长表明配合物1和2中的铁(Ⅱ)在低自旋状态。在[Fe(L)3]2+中, 相邻配体中的苯环和咪唑环形成分子内π-π相互作用。配合物1和2通过分子间C-H…π相互作用形成三维超分子结构。CD光谱证实配合物1和2在溶液中的光学活性。磁性测试表明配合物1和2分别在232和250 K发生自旋转换。由于配合物1和2具有相同的手性空间群和类似的堆积方式和分子间相互作用, 导致1和2表现出不同自旋转换温度的原因主要是取代基效应。

English

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  • 收稿日期:  2014-10-17
  • 网络出版日期:  2014-11-10
通讯作者: 陈斌, bchen63@163.com
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