有机化学 ›› 2018, Vol. 38 ›› Issue (12): 3386-3393.DOI: 10.6023/cjoc201805012 上一篇    下一篇

研究简报

含间苯二甲酰胺基的大环合成及其对阴离子的识别研究

魏小康, 谷静池, 刘兴丽, 黄超, 朱必学   

  1. 贵州大学大环及超分子化学重点实验室 贵阳 550025
  • 收稿日期:2018-05-03 修回日期:2018-07-09 出版日期:2018-12-25 发布日期:2018-08-14
  • 通讯作者: 朱必学 E-mail:bxzhu@gzu.edu.cn
  • 基金资助:

    贵州省科技厅、贵州大学联合项目(No.LH[2017]7256)和教育部春晖计划(No.Z2016009)资助项目.

Synthesis and Anion Recognition of Macrocycle Containing Isophthalamide Unit

Wei Xiaokang, Gu Jingchi, Liu Xingli, Huang Chao, Zhu Bixue   

  1. Key Laboratory of Macrocyclic and Supramolecular Chemistry, Guizhou University, Guiyang 550025
  • Received:2018-05-03 Revised:2018-07-09 Online:2018-12-25 Published:2018-08-14
  • Contact: 10.6023/cjoc201805012 E-mail:bxzhu@gzu.edu.cn
  • Supported by:

    Project supported by the Joint Project of Science and Technology Department of Guizhou Province (No. LH[2017]7256) and the "Chun-Hui" Fund of Ministry of Education (No. Z2016009)

通过Schiff碱缩合成环作用,从NN'-(6-胺基-2-吡啶基)-1,3-二甲酰亚胺苯和5,5'-亚甲基双水杨醛反应制备得到同时含间苯二甲酰胺单元及酚环的[1+1]Schiff碱大环L.采用1H NMR、FABMS和元素分析等手段对大环的组成进行了表征.通过X射线单晶衍射技术解析了大环L的晶体结构,结构分析表明,大环分子具有折叠钳式结构,在晶态结构中大环分子间通过氢键、π…π堆积作用自组装为具有1D槽的柱阵列结构.通过紫外-可见吸收光谱滴定技术对大环与系列阴离子的键合作用考察,结果表明大环L对H2PO4-、HP2O73-具有识别作用.进一步通过紫外-可见吸收光谱、核磁和等温量热滴定等技术对大环L分别与H2PO4-、HP2O73-阴离子的识别反应进行了考察,获得了识别反应的配位比、平衡常数(K)及△rHm、△rSm、△rGm等热力学参数信息.结果表明,大环L与H2PO4-形成键合比为1:1的配合物,与HP2O73-形成键合比为2:1的夹心式配合物结构.

关键词: 间苯二甲酰胺, 酚环, Schiff碱大环, 阴离子, 识别

A[1+1] Schiff base macrocyclic compound L containing isophthalamide unit and phenol rings has been synthesized from the reaction of precursors N,N'-(6-amino-2-pyridyl)-1,3-dicarboximide with 5,5'-methylene bis-salicylaldehyde by Schiff-base condensation. The macrocycle L was characterized via 1H NMR, FABMS, and elemental analysis. The crystal structure of L was determined by X-ray diffraction analysis, and it has a folded clamp conformation. In the crystal state of L, individual macrocycles were assembled into columnar structures with 1D channel through intermolecular hydrogen bonding and π-π stacking interactions. The results show that the macrocycle L displays a selective recognition ability for H2PO4- and HP2O73- anion respectively by the coordination reaction of L with a series of anions using UV-Vis absorption spectra technique. Furthermore, the coordination reaction of L with H2PO4- or HP2O73- anion was investigated via UV-Vis spectra, 1H NMR and the isothermal titration calorimeter (ITC) respectively. The stoichiometric ratio, the association constant (K) and the thermodynamic parameters (△rHm, △rSm and △rGm) of the coordination reaction were obtained. The results show that the macrocycle L binds H2PO4- with a 1:1 binding stoichiometry, and binds HP2O73- to form the structure of sandwich-type with a bonding ratio of 2:1.

Key words: isophthalamide, phenol ring, Schiff-base macrocycle, anion, recognition