高等学校化学学报 ›› 2020, Vol. 41 ›› Issue (1): 70-77.doi: 10.7503/cjcu20190310

• 研究论文:无机化学 • 上一篇    下一篇

无机-有机杂化化合物[(H2DABCO)CuCl4]·H2O的合成及开关型介电性质

秦刘磊,刘洋(),关小琴,郑晓媛,张子钰,刘尊奇()   

  1. 新疆农业大学化学工程学院, 乌鲁木齐 830052
  • 收稿日期:2019-05-30 出版日期:2019-01-10 发布日期:2019-11-04
  • 通讯作者: 刘洋,刘尊奇 E-mail:daidaishu85@163.com;zunqi85@163.com
  • 基金资助:
    国家自然科学基金批准号:(21561030);新疆农业大学研究生科研创新项目资助批准号:(XJAUGRI2018029)

Synthesis and Switchable Dielectric Properties of an Inorganic-organic Hybrid Complex [H2(DABCO)CuCl4]·H2O

QIN Liulei,LIU Yang(),GUAN Xiaoqin,ZHENG Xiaoyuan,ZHANG Ziyu,LIU Zunqi()   

  1. Chemical Engineering College, Xinjiang Agricultural University, Urumqi 830052, China
  • Received:2019-05-30 Online:2019-01-10 Published:2019-11-04
  • Contact: Yang LIU,Zunqi LIU E-mail:daidaishu85@163.com;zunqi85@163.com
  • Supported by:
    ? Supported by the National Natural Science Foundation of China No(21561030);the Graduate Research Innovation Project of the Xinjiang Agricultural University, China No(XJAUGRI2018029)

摘要:

将1,4-二氮杂二环[2.2.2]辛烷(DABCO)、 二水合氯化铜和盐酸溶于甲醇-水混合溶剂中, 通过常温蒸发法制备了一个新颖的无机-有机杂化化合物[(H2DABCO)CuCl4]·H2O(1). 利用红外光谱(IR)、 X射线粉末衍射(XRD)、 单晶X射线衍射、 元素分析、 热重分析(TG)、 变温-变频介电分析等对化合物1进行结构表征及性质测试. 在低温(100 K)和室温(294 K)下, 该化合物属于单斜晶系P21/c空间群, 在bc平面内, 通过N—H…O, O—H…Cl等氢键自组装作用形成二维网状结构. 而铜离子在c轴上的相对位移导致化合物1在多轴方向呈现出明显的开关型介电异常峰, 变温-变频介电常数沿不同晶轴呈显著的各向异性.

关键词: 晶体结构, 氢键, 无机-有机杂化化合物, 介电各向异性

Abstract:

A novel inorganic-organic hybrid complex, [H2(DABCO)CuCl4]·H2O(1), was successfully synthesized via the reaction of 1,4-diazabicyclo[2.2.2]octane, copper(Ⅱ) chloride dihydrate and hydrochloric acid. The complex was characterized by single-crystal X-ray diffraction, IR spectra, powder X-ray diffraction analysis, thermogravimetric analysis and variable-temperature dielectric measurement. Single crystal XRD analysis reveals that compound 1 belongs to monoclinic space group P21/c at low temperature and room temperature, and the unit cell parameters a, b, c, and V change significantly from low temperature to room temperature for the same structure phase transition. The single crystal structure shows that a two-dimensional network is formed in the bc plane through N—H…O and O—H…Cl hydrogen bonding interactions. The relative displacement of copper ions along the c-axis leads to switchable dielectric abnormal peaks and temperature dependence of its dielectric permittivity displays remarkable dielectric anisotropy along different crystal axes.

Key words: Crystal structure, Hydrogen bond, Inorganic-organic hybrid complex, Dielectric anisotropy

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