高阶柱芳烃的制备及其主客体化学的研究

发布时间：2018-06-04 21:40

本文选题：超分子化学 + 柱芳烃　；参考：《浙江大学》2017年博士论文

【摘要】：大环主体化合物是推动超分子化学迅猛发展的重要力量。继冠醚、环糊精、杯芳烃和葫芦脲之后,作为新一代大环主体的柱芳烃自2008年被报道以来,一直受到超分子化学家们的持续关注,经过近十年的发展,柱芳烃已经在超分子化学的舞台上展现了无限的风采和魅力。作为柱芳烃的重要组成部分,高阶柱芳烃具有不同于传统柱[5]芳烃和柱[6]芳烃的拓扑学结构和主客体性质,然而对于高阶柱芳烃的研究尚处不够深入。本论文首先概述了高阶柱芳烃的发展现状,然后重点阐述了水溶性柱[7]芳烃和柱[9]芳烃的合成,主客体化学性质及其在超分子自组装方面的相关研究工作。本论文的正文部分包括以下四个部分:在第一部分工作中,我们第一次制备出了阴离子型水溶柱[7]芳烃,并研究了其与紫精客体的主客体络合性质。1HNMR、ESI-MS、NOESY、UV-Vis以及荧光实验证明主体和客体在水中形成1:1[2]准轮烷,并且由于多重静电相互作用,其络合常数高达(2.96±0.31)×109 M-1。由于羧酸根阴离子的特性,该主客体络合物具有酸碱响应性,通过加酸加碱,可以简单地控制该络合物的解络合与再络合。这一新的主客体识别体系被进一步用于构筑超分子两亲体系,通过主客体作用,可以实现组装体从胶束向囊泡的转变。在第二部分工作中,我们第一次制备出了阴离子型水溶柱[9]芳烃,并且也研究了它与紫精客体的酸碱响应性主客体性质。通过实验证明主客体在水溶液中自组装成1:1包结络合物,其络合常数有(2.27±0.24)× 106 M-1。相比较于前一部分的水溶性柱[7]芳烃,络合常数的减小是因为柱[9]芳烃的内部空腔尺寸比柱[7]芳烃的大,与紫精客体的尺寸匹配性没有柱[7]芳烃好。在第三部分工作中,我们基于水溶性柱[9]芳烃与2,7-氮杂芘衍生物建立了一种新型的具有双向酸碱响应性的主客体识别机理。因为水溶性柱[9]芳烃对盐酸和氢氧化钠具有可逆响应性,而2,7-氮杂芘衍生物对正己胺和三氟乙酸具有可逆响应性,所以我们不仅利用盐酸/氢氧化钠这一酸碱对,而且可以利用正己胺/三氟乙酸这一碱酸对来实现对主客体络合物的解络合与再络合的控制,使该络合物成为具备双向酸碱响应性的分子开关。在第四部分工作中,我们研究了阴离子型水溶性柱[7]芳烃与2,7-氮杂芘衍生物之间的酸碱响应性主客体络合性质。基于这一主客体识别机理,我们构筑了一个新的超分子两亲体系。通过主客体络合作用,我们可以方便地调控组装体在水中的形貌。另外,由于水溶性柱[7]芳烃具有酸碱响应性,我们可以通过简单地加酸加碱操作来可逆地控制主体客体络合与解络合的状态,从而达到可逆控制超分子两亲自组装体形貌的目的。
[Abstract]:Macrocyclic host compounds are important forces to promote the rapid development of supramolecular chemistry. After crown ethers, cyclodextrins, calixarenes and cucurbiturides, column aromatics, as the new generation of macrocyclic aromatic hydrocarbons, have been continuously concerned by supramolecular chemists since they were reported in 2008. Column aromatics have shown infinite charm and charm on the stage of supramolecular chemistry. As an important component of column aromatics, high-order aromatics have different topological structures and host and guest properties from traditional [5] aromatics and column [6] aromatics. In this paper, the development of high order column aromatics is reviewed, and the synthesis, host and guest chemical properties of water-soluble [7] aromatics and column [9] aromatics and their research work in supramolecular self-assembly are discussed. The main body of this thesis includes four parts as follows: in the first part, we prepared anion water soluble column [7] aromatics for the first time. The host and guest complexation properties of the host and guest with purple spermatine were studied. 1HNMRESI-MSI NOESYVis and fluorescence experiments showed that the host and guest formed 1:1 [2] quasi rotorane in water, and its complexation constant was as high as 2.96 卤0.31 脳 109M-1 due to the multiplex electrostatic interaction. Because of the characteristic of carboxylate anion, the host and guest complex is acid-base responsive. By adding acid and alkali, the uncomplexation and recomplexation of the complex can be controlled simply. This new host and guest recognition system is further used to construct a supramolecular amphiphilic system, through which the assembly can be transformed from micelle to vesicle. In the second part, we prepared anion soluble column [9] aromatics for the first time, and also studied the acid-base responsive host and guest properties of the anion column [9] aromatics. It is proved by experiments that the host and guest self-assemble into 1:1 inclusion complex in aqueous solution, and its complexation constant is 2.27 卤0.24) 脳 106M-1. Compared with the water-soluble column [7] aromatics in the former part, the complexation constant decreases because the inner cavity size of [9] aromatics is larger than that of column [7] aromatics, and the size matching with the column [7] aromatics is not as good as that of column [7] aromatics. In the third part, based on the water-soluble column [9] aromatics and 2O7-azapyrene derivatives, a novel host-guest recognition mechanism with bidirectional acid-base response was established. Because the water-soluble column [9] arene has reversible response to hydrochloric acid and sodium hydroxide, while the derivative of 2O7-azapyrene has reversible response to n-hexylamine and trifluoroacetic acid, we not only use hydrochloric acid / sodium hydroxide as acid-base pair, The alkali-acid pair of n-hexylamine / trifluoroacetic acid can be used to control the uncomplexation and recomplexation of the host and guest complex, which makes the complex become a molecular switch with bidirectional acid-base response. In the fourth part, we have studied the acid-base responsive host and guest complexing properties between [7] aromatics and 2O7-azapyrene derivatives. Based on the host and guest recognition mechanism, a new supramolecular amphiphilic system is constructed. Through the host and guest complexation, we can easily control the morphology of the assembly in water. In addition, due to the acid-base response of water-soluble column [7] aromatics, we can control the complexation and desorption state of the host and guest by simply adding acid and alkali. In order to achieve the purpose of reversible control of supramolecular self-assembly morphology.
【学位授予单位】：浙江大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O641.3

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