摘要/Abstract

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^-、HP₂O₇^3-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^-、HP₂O₇^3-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△_rH_m、△_rS_m、△_rG_m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HP₂O₇^3-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 HP₂O₇^3- 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 HP₂O₇^3- 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 (△_rH_m, △_rS_m and △_rG_m) of the coordination reaction were obtained. The results show that the macrocycle L binds H₂PO₄^- with a 1:1 binding stoichiometry, and binds HP₂O₇^3- 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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