高等学校化学学报

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一维链状氢键型甘氨酸超分子化合物[(Gly)2+ (18-crown-6)2(MnCl4)2‒的合成、 结构及介电性质

王乐, 秦刘磊, 刘洋(), 任丽, 徐慧婷, 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:2020-08-24
  • 通讯作者: 刘洋,刘尊奇 E-mail:liuyangxj85@163.com;zunqi85@163.com
  • 基金资助:
    国家自然科学基金(21561030);新疆维吾尔自治区研究生科研创新项目(XJ2020G162)

Synthesis, Structure and Dielectric Properties of One-dimensional Chain Hydrogen Glycine Supramolecular Compound [(Gly)2+(18-crown-6)2(MnCl42‒

WANG Le, QIN Liulei, LIU Yang(), REN Li, XU Huiting, LIU Zunqi()   

  1. Chemical Engineering College,Xinjiang Agricultural University,Urumqi 830052,China
  • Received:2020-08-24
  • Contact: LIU Yang,LIU Zunqi E-mail:liuyangxj85@163.com;zunqi85@163.com
  • Supported by:
    ? Supported by the National Natural Science Foundation of China(21561030);the Postgraduate Scientific Research Innovation Project of Xinjiang Uygur Autonomous Region, China(XJ2020G162)

摘要:

以甘氨酸(Gly)、 18-冠醚-6、 二氯化锰(MnCl2)和盐酸为原料, 通过蒸发法获得一种新型相变一维链状氢键型甘氨酸超分子化合物[(Gly)2+ (18-crown-6)2(MnCl4)2?](1). 通过元素分析、 变温X射线单晶衍射和介电测试等手段对其进行了表征和解析. 实验结果表明, 该晶体属于单斜晶系, 空间群从P21/c(100 K)转化为C2/c(293 K). 随着温度升高, [MnCl4]2?呈现无序状态的共棱双四面体结构. 质子化甘氨酸分子和分子内羟基(—OH)发生动态摆动, 引起O—HCl型一维氢键链产生明显伸缩运动, 导致化合物1在一定温度范围内出现结构相变及介电异常.

关键词: 氢键, 分子摆动, 金属配合物, 结构相变, 阶梯状介电

Abstract:

A new phase transition one-dimensional chain hydrogen-bonding glycine supramolecular [(Gly)2+(18-crown-6)2(MnCl42?](1) was prepared by evaporation method with the reaction of glycine(Gly), 18-crown-6, transition metal compound MnCl2 and hydrochloric acid. Compound 1 was characterized and analyzed by means of elemental analysis, variable temperature X-ray single crystal diffraction and dielectric constant measurements. The results showed that crystal of the title complex belonged to monoclinic crystal system, space group changed from P21/c(100 K, low temperature) to C2/c(293 K, room temperature). [MnCl42? anion displayed a double tetrahedral structure with common edges in a disordered state with the temperature increasing. Dynamic oscillations occured between the protonated glycine molecule and the intramolecular hydroxyl group(—OH), and built one-dimensional O—HCl hydrogen bonds chain with obvious stretching motion. These caused the structural phase transition and dielectric anomaly of compound 1 in a certain temperature range.

Key words: Hydrogen bond, Molecular swing, Metal complex, Structural phase transition, Stepped dielectric anomaly

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