含间苯二甲酰胺基的大环合成及其对阴离子的识别研究
收稿日期: 2018-05-03
修回日期: 2018-07-09
网络出版日期: 2018-08-14
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
Received date: 2018-05-03
Revised date: 2018-07-09
Online published: 2018-08-14
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N，N'-（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.
魏小康 , 谷静池 , 刘兴丽 , 黄超 , 朱必学 . 含间苯二甲酰胺基的大环合成及其对阴离子的识别研究[J]. 有机化学, 2018 , 38(12) : 3386 -3393 . DOI: 10.6023/cjoc201805012
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
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