氢键等分子间作用力构建的杯芳烃纳米管

发布时间：2018-01-08 23:24

本文关键词：氢键等分子间作用力构建的杯芳烃纳米管　出处：《武汉大学》2015年博士论文　论文类型：学位论文

【摘要】：杯芳烃本身具有疏水性的空腔,能通过自身的反应位点引入不同的官能团,通过主客体分子间多种非共价键作用力形成的超分子聚集体,在气体吸附、模拟酶催化、药物载体、纳米材料和富勒烯化学等方面得到了广泛的应用。然而目前基于杯芳烃的自组装体及其形成的纳米管的报道仍然不多,对杯芳烃自组装机理也了解甚少。本论文在实验室以前工作的基础之上,进一步深入地研究拥有不同构象和不同作用位点的杯[4]芳烃和硫杂杯[4]芳烃通过非共价键作用力形成纳米管的自组装行为。第一章首先介绍了超分子化学和主客体化学,接着较为详细地介绍了杯[4]芳烃主体分子的结构、构象及其衍生化反应,最后总结了通过非共价键作用力作为驱动力,包括氢键、π…π堆积作用和金属配位键等,形成杯[4]芳烃纳米管的研究进展。第二章合成了上缘含醛基、氰基和羧基基团的不同构象的杯[4]芳烃衍生物,上缘含醛基、氰基和羟基的锥式构象的硫杂杯[4]芳烃衍生物和上缘含醛基的部分锥式构象的硫杂杯[4]芳烃衍生物。通过最终的反应产物推测出杯[4]芳烃下缘异丙基的脱去是在醛基引入到杯芳烃上缘之后进行的。通过研究柱[5]芳烃反应的中间产物并结合文献分析,验证了Holler提出柱[5]芳烃的合成是通过阳离子反应机理的合理性。第三章研究了没有强氢键授受体存在的情况下,用氯仿/环己烷作为结晶溶剂,不同构象的硫杂杯[4]芳烃衍生物的自组装行为。与杯[4]芳烃相比,桥联S原子取代C原子使硫杂杯[4]芳烃拥有更大的空腔,更容易形成“头对头,,的二聚体结构；S原子形成的S…π和S…S等作用力能有效协助晶体进行自组装。结果显示：锥式构象的醛基硫杂杯[4]芳烃衍生物都通过分级拼接的方式形成了“头对头”的二聚体和蜂窝状的纳米管结构；锥式构象的氰基硫杂杯[4]芳烃衍生物在无法形成二聚体的情况下,通过与氯仿分子间的Cl…π、N…Cl和Cl…Cl作用力也形成了蜂窝状的纳米管结构；部分锥式构象的醛基硫杂杯[4]芳烃衍生物由于苯环倒置减少了环腔间的排斥,形成了“头对头”二聚体和蜂窝状的纳米管结构；下缘乙酸乙酯和苯甲酰基四取代的1,3-交替构象的硫杂杯[4]芳烃衍生物能通过S…π或S…S作用力以“肩并肩”的方式进行连接,形成沿杯芳烃环腔堆积的纳米管结构。从这些我们可以看出,主体分子的构象不是分子能否构成纳米管的决定因素,在分子骨架上引入适当的基团,并在合适的结晶环境下通过分子间的相互作用力能以恰当的排列方式形成纳米管。第四章研究了杯芳烃上缘存在强氢键授受体的情况下,分别用吡啶/甲醇和四氢呋喃/甲醇作为结晶溶剂,不同构象的杯[4]芳烃羧酸衍生物(羧酸数目≥2)自组装行为。锥式构象的杯[4]芳烃羧酸衍生物的羧基位于杯芳烃的同一侧,可以与其它主体分子和溶剂分子形成不同类型的氢键作用力;当同侧连有羧基的苯环向环腔收缩(二面角小于30°,杯芳烃分子倾向于形成由自身的两对羧基构成的氢键二聚体结构,当连有羧基的苯环向环外扩张,相邻的主体分子会形成由一对羧基间氢键构成的一维波浪结构。部分锥式和1,3-交替构象的杯[4]芳烃羧基衍生物,由于羧基在两侧,可以直接或者在溶剂的帮助下形成一维波浪形或者链状的结构。溶剂分子对自组装行为产生影响,吡啶容易通过O-H…N氢键形成“头对头”的二聚体结构,主导分子的自组装;四氢呋喃体现的是一个协助作用,填充在晶体所形成的空隙中；在缺少强氢键作用点的情况下,甲醇可以作为一个补充的氢键作用位点与主体分子间以“头对头”或“肩并肩”的方式相连接。第五章研究了没有强氢键授受体和S硫原子存在的情况下,不同构象的杯[4]芳烃衍生物的自组装行为。由于超分子作用点比较少,杯芳烃在分子间的弱相互作用力,如C-H…O、C-H…π和O…π等,协助下通过分子间紧密堆积的方式形成超分子网络结构。下缘取代基的位阻效应会影响杯[4]芳烃衍生物产生不同的自组装行为。当下缘没有取代基时,锥式构象的醛基杯[4]芳烃容易以分级拼接方式形成纳米管；当下缘的取代基为柔性较大的正丙基时,1,3-交替构象杯[4]芳烃四醛分子为了有效降低相邻分子之间的排斥力,分子发生了90°的旋转,通过两组相互垂直的醛基形成三维的C-H…O氢键,沿着分子环腔方向堆积形成了一维纳米通道；当下缘的取代基为位阻较大的异丙基时,1,3-交替构象杯[4]芳烃醛基衍生物的醛基向环腔内收缩,分子间通过密堆积形成三维结构；在杯[4]芳烃的上缘引入氰基或者下缘引入苯甲酰基可以提供不同类型的超分子作用点,协助杯芳烃聚集体的生成。
[Abstract]:The calixarene cavity itself is hydrophobic, through the reaction sites themselves into different functional groups, the main object of intermolecular non covalent bond interaction of various supramolecular aggregates formed in the gas, adsorption, mimic enzyme catalysis, drug carrier, nano materials and fullerene chemistry has been widely used. However, self assembling cup the aromatic body and the formation of nanotubes is reported based on still not much, little of the calixarene self-assembly mechanism. This paper also understand based on previous work in the laboratory, further study the self-assembly behavior with different conformation and different sites of Calix [4] arene and thiacalix [4] arene through non covalent interactions to form nanotubes. The first chapter introduces the supramolecular chemistry and host guest chemistry, then describes in detail the structure of Calix [4] arene molecular structure. In the end, the effects of the non covalent bond force as the driving force, including the hydrogen bond, pi... PI stacking interactions and metal ligand bond, the advances in research on the formation of Calix [4] nanotubes. The upper edge of the second chapter containing aldehyde synthesis, calix [4] arene derivatives of different conformation of cyano group and carboxyl groups, on the border with aldehyde, cone conformation cyano and hydroxyl on the sulfur partial cone conformation of Calix [4] aromatic derivatives and the upper edge of the containing aldehyde thiacalix [4] arene derivatives. The final reaction products that remove calix [4] arene is in the lower edge of isopropyl aldehyde into after the calixarene margin. The intermediate of pillar [5] arene reaction and combined with literature analysis, verification the synthesis of Holler of pillar [5] arene through reasonable cationic reaction mechanism. The third chapter studies the strong hydrogen bond acceptor without the presence of chloroform / cyclohexane as solvent crystallization, different conformations of thia self-assembly of Calix [4] arene derivatives Behavior, compared with calix [4] arene, bridged S atoms instead of C atoms make the calix [4] aromatics have larger cavities, easier to form the "head pair", the two polymer structure, and the S formed by S atoms. PI and S... S force can effectively assist crystal self-assembly. The results showed that the sulfur aldehyde cone conformation thiacalix [4] arene derivatives through the classification mosaic and formed a "nanotube structure two dimers and honeycomb head"; the sulfur cyano cone conformation thiacalix [4] arene derivatives in not formation two dimers, with chloroform molecules Cl... PI, N... Cl and Cl... Cl force also formed a honeycomb tube structure; aldehyde sulfur part cone conformation thiacalix [4] arene derivatives of benzene ring cavity reduces the inversion due to the repulsion between, forming a nanotube structure two head to head dimer and honeycomb; the lower edge of ethyl acetate and four benzoyl substituted 1,3- alternate conformation thiacalix [4] arene derivatives by S... PI or S... S forces are connected by "side by side", the formation of nanotubes deposited along the calixarene ring cavity. From these we can see, the main molecular conformation of the molecular determinants is not whether nanotubes, appropriate groups were introduced into the backbone, and in the crystallization environment suitable to the appropriate arrangement the nanotubes are formed by intermolecular interactions. The fourth chapter studies the calixarene strong hydrogen bond acceptor edge exist, respectively with pyridine / methanol and tetrahydrofuran / methanol as solvent, calix [4] arene carboxylic acid derivatives with different conformation (carboxylic acid number = 2). The self-assembly behavior of Calix [4] arene carboxylic acid derivatives cone the conformation of carboxyl in calixarene on the same side, can form hydrogen bonds with other different types of host molecules and solvent molecules; when the same side connected with carboxyl phenyl ring to the ring cavity The contraction (dihedral angle less than 30 degrees, calixarene molecules tend to form by the two to a two mer carboxyl hydrogen bond structure, even when the carboxyl benzene ring to ring expansion body adjacent molecules formed by a pair of carboxyl hydrogen bonds between a one-dimensional wave structure. Some cone and 1,3- alternate conformation calix [4] arene carboxylic acid derivatives, carboxyl on both sides, either directly or in a solvent with the help of forming a one-dimensional wave shaped or chain structure. The solvent molecules on the self-assembly behavior is influenced by pyridine easily through O-H... N hydrogen bonds formed "head to head" two dimeric structure, dominant molecular self-assembly; tetrahydrofuran is a manifestation of help, void filling formed in the crystal; in the absence of strong hydrogen bonding points, methanol can be used as a supplement to the main intermolecular hydrogen bonding site and to "head right" or "side by side" is connected. The fifth chapter studies did not grant strong hydrogen bond receptor and S sulfur atoms exist, the self-assembly behavior of Calix [4] arene derivatives with different conformations. The supramolecular interaction points less, calixarene interaction in intermolecular weak, such as C-H... O, C-H... PI and O... PI, by way of inter molecular close packing of the assistance of forming supramolecular network structure. The steric effect of substituents will affect the lower edge of Calix [4] arene derivatives have different self-assembly behaviors. The present margin of no substituent, aldehyde calix [4] arene cone conformation easy to splice form classification of nanotubes; replace the edge of the base for large flexible propyl, 1,3- alternate conformation of Calix [4] arene four aldehyde molecules in order to effectively reduce the repulsive force between adjacent molecules, molecules in the 90 degree rotation, the formation of three-dimensional C-H through two mutually orthogonal sets of aldehyde... O hydrogen bonds along the molecular ring cavity accumulated to form one-dimensional nano channel; substituent present margin for large steric effect of isopropyl, aldehyde 1,3- alternate conformation of Calix [4] arene derivatives to aldehyde ring cavity contraction molecules through close packed into a three-dimensional structure; in the [4] cup on the edge of the introduction of aromatic hydrocarbons or the lower edge of the introduction of cyano benzoyl can provide different types of supramolecular interactions, assist in the generation of calixarene aggregates.

【学位授予单位】：武汉大学
【学位级别】：博士
【学位授予年份】：2015
【分类号】：O625;TB383.1

【参考文献】