高等学校化学学报 ›› 2019, Vol. 40 ›› Issue (5): 873-879.doi: 10.7503/cjcu20180827

• 无机化学 • 上一篇    下一篇

具有三核Cd(Ⅱ)簇单元和螺旋链的脯氨酸类单一手性金属-有机框架材料的合成、 结构和性质

徐中轩(), 黄丽娜, 邓玉花, 蒙琴   

  1. 遵义师范学院化学化工学院, 遵义 563002
  • 收稿日期:2018-12-10 出版日期:2019-04-19 发布日期:2019-03-27
  • 作者简介:

    联系人简介: 徐中轩, 男, 博士, 教授, 主要从事功能配合物研究. E-mail: xuzhongxuan4201@163.com

  • 基金资助:
    国家自然科学基金(批准号: 21761036)、 贵州省自然科学基金(批准号: 20181182)和贵州省教育厅“125”计划专项基金(批准号: 2012015)资助.

Syntheses, Structures and Properties of Homochiral Metal-organic Frameworks with Helices and Trinuclear Cluster Units Based on Semirigid Proline Derivatives

XU Zhongxuan*(), HUANG Lina, DENG Yuhua, MENG Qin   

  1. School of Chemistry and Chemical Engineering, Zunyi Normal College, Zunyi 563002, China
  • Received:2018-12-10 Online:2019-04-19 Published:2019-03-27
  • Contact: XU Zhongxuan E-mail:xuzhongxuan4201@163.com
  • Supported by:
    † Supported by the National Natural Science Foundation of China(No.21761036), the Natural Science Foundation of Guizhou Province, China(No.20181182) and the “125” Program of Guizhou Education Department, China(No.2012015).

摘要:

在溶剂热反应条件下, 使用含氮辅助配体1,4-二(4-吡啶基)苯(1,4-DPB)和半刚性脯氨酸衍生物配体(R)-5-(2-羧基吡咯烷-1-羰基)间苯二甲酸[(R)-H3PIA]或(S)-5-(2-羧基吡咯烷-1-羰基)间苯二甲酸[(S)-H3PIA]与Cd2+构筑了单一手性金属-有机框架材料[Cd1.5((R)-PIA)(1,4-DPB)1.5]·0.75H2xGuest(1-D)和[Cd1.5((S)-PIA)(1,4-DPB)1.5]·0.75 H2xGuest(1-L). 配合物1-D和1-L呈具有开放孔道的三维柱层式框架结构, 含有三核镉簇单元 Cd3(CO2)6与两种螺旋链构建的波浪形Cd-PIA层. 分别对上述化合物进行了粉末X射线衍射、 热重分析、 圆二色谱和荧光光谱等测试. 测试结果显示配合物1-D和1-L都是以纯晶体的形式存在, 2种配合物的热失重曲线接近, 圆二色谱有明显的正负吸收峰, 符合其对映体的结构特征.

关键词: 单一手性, 脯氨酸衍生物, 金属-有机框架, 螺旋链, 镉簇

Abstract:

With the help of nitrogen heterocycle auxiliary ligand 1,4-di(pyridin-4-yl)benzene)(1,4-DPB), a pair of homochiral metal-organic frameworks named [Cd1.5((R)-PIA)(1,4-DPB)1.5]·0.75H2xGuest(1-D) and [Cd1.5((S)-PIA)(1,4-DPB)1.5]·0.75 H2xGuest(1-L)[H3PIA=5-(2-carboxypyrrolidine-1-carbonyl)isophthalic acid] have been prepared from proline derivative ligands (R)-H3PIA and (S)-H3PIA and cadmium ions. Crystallographic analysis indicates that complexes 1-D and 1-L feature three-dimensional open pore structure, containing wavy metal-carboxylate layers and almost linear trinuclear cadmium cluster units. In complexes 1-D and 1-L, the wavy metal-carboxylate layers consists of two types of homochiral helical chains, which are constructed by PIA fragments and cadmium ions. Moreover, powder X-ray diffraction patterns(PXRD), thermogravimetric analysis(TGA), circular dichroism(CD) spectra, and photoluminescent spectra of complexes 1-D and 1-L were also investigated. The results show all the peak positions of simulated and experimental PXRD patterns match well with each other, indicating that the complexes were obtained as a single phase. Furthermore, TGA curves of complexes 1-D and 1-L are very similar to each other and their CD spectrum have obviously positive or negative signal, which accord with their enantiomeric properties.

Key words: Homochirality, Proline derivative, Metal-organic framework, Helical chain, Cadmium cluster

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