【作者】 徐炯；

【导师】 苏纪豪； 李炜；

【作者基本信息】 天津大学 ， 药学硕士（专业学位）， 2021， 硕士

【摘要】 超分子化学是近年来的热门话题,主要研究分子之间的作用力和主客体结合等;作为主体的大环化合物是该领域的重要研究对象,其特殊的结构和性质被广泛应用各个领域,通过合成新的大环而开发新的主体是超分子化学领域中具有挑战性的项目。本文在总结柱[5]芳烃的文献基础上,对于其部分氧化衍生物柱[4]芳烃[1]醌和冕[5]芳烃做了进一步修饰,并将所得到的四种新型大环分子进行了结构表征。第一章首先简要介绍了柱[5]芳烃的裸骨架——[1_n]对环烷大环的结构和性质,包括柱[n]芳烃,领[n]芳烃以及冕[n]芳烃等。其中柱[5]芳烃近年来以其合成的便捷性以及特殊的主客体的性质而受到广泛关注。采取柱[5]芳烃作为研究对象的原因有以下几点:第一,柱[5]芳烃以[1_n]对环烷为裸骨架与其电子云排布较为类似;第二,在柱[5]芳烃的基础上,通过对其修饰而得到的一系列新型大环分子具有完全不同的性质及结构拓展;第三,柱[5]芳烃的结构是坚固的五边形柱型分子。综上,为了开发新的大环分子,本文的主要研究对象为柱[5]芳烃部分氧化产物柱[4]芳烃[1]醌和边缘化修饰的产物冕[5]芳烃。第二章主要介绍了柱[5]芳烃部分氧化和过氧化产物的提出和发展过程,包括其合成方法,结构性质和在此基础上可以实现的进一步的衍生化并形成全新大环化合物,包括还原并再次修饰而形成[4+1]模式的共柱[5]芳烃等。柱[5]芳烃部分氧化的产物之一——柱[4]芳烃[1]醌,由于引入了苯醌单元,其电子云排布出现了改变但原有的柱型结构却得以保留;这使得柱[4]芳烃[1]醌同样成为重要的大环主体化合物。实验目的是对柱[4]芳烃[1]醌进行进一步修饰并得到全新的大环化合物;实验方法采用1,3-丁二烯对其进行狄尔斯-阿尔德反应,分离主要产物进行结构表征。实验结果显示,起始物醌单元上的双键会进行有选择性地与醌单元的单边发生加成反应;X光晶体衍射的结果显示,经过本次修饰的新型大环分子DA-1无法保持类似柱芳烃的柱型结构,一个与被修饰的醌单元相邻的苯环单元呈现水平状态,即五边形柱形结构被破坏;与此同时,溶剂分子的引入会对大环分子提供构象转换的动力,乙腈分子可以进入大环内部并将水平的苯环单元推出,而实现构象转换并扩张大环内部的直径;此转换过程也可以通过用不同氘代溶剂的核磁共振波谱证明。得出结论,此举合成的新型大环破坏原本坚固的五边形柱状结构以及原本的对称性,使其展现出截然不同的分子构型。第三章的内容介绍了衍生于边缘化修饰的柱[5]芳烃的新型大环——冕[5]芳烃,包括其设计思路,合成步骤,分子结构和相关性质。本章所介绍的三种新型大环分子是通过铃木-宫浦偶联反应修饰的冕[5]芳烃衍生物。实验目的是通过形成碳-碳单键,对进冕[5]芳烃行修饰;实验方法采取三种苯硼酸对冕[5]芳烃进行修饰;实验结果显示,三种衍生物已被成功合成,并通过核磁和质谱对其进行结构鉴定;得出结论此举不仅在冕[5]芳烃的基础上开发了新的大环主体,更是为冕[5]芳烃增加了“二层结构”使其结构更加具有柔韧性,可以为更为复杂3D结构提供潜在的基础单元。第四章是对文章中所介绍的新合成的分子所作出的总结和展望。由于冕[5]芳烃衍生物包含的五重对称轴,将在超分子化学领域的研究起到重要作用。第一,根据柏拉图多面体的形成规则,可以为构建金属有机或共价有机分子十二面体,提供了潜在的五重对称基础模块;第二,冕[5]芳烃的二层结构增加了分子的深度,可以以此为基础合成深穴大环分子;第三,将冕[5]芳烃的二层结构苯环与原有的骨架通过一定条件缩合,可为合成纳米带提供全新的思路。更多还原

【Abstract】 Supramolecular chemistry is a hot issue in recent years,it mainly studies the interaction between molecules and host-guest interactions;macrocyclic compounds as“hosts” are significant research objects in this field,because of their special structures and properties which can be widely applied in various fields.So far,the development of synthesizing new macrocycles is still a challenging project.Herein,this thesis mainly introduces the four derivatives of pillar[4]arene[1]quinone and tiara[5]arene which are derived from pillar[5]arenes.In Chapter 1,the basic skeleton of pillar[5]arene—[1n]paracyclophanes were briefly introduced,including their structure and related properties.Based on the same basic skeleton,a series of macrocycles like pillar[n]arene,collar[n]arene and tiara[n]arene also were mentioned.Among them,pillar[5]arenes have drawn extensive attention in recent years due to their ease of synthesis and their special properties.The reasons for adopting pillar[5]arenes as the research object of this thesis are as follows: 1)regarding pillar[5]arenes as starting materials can obtain [1n]PCPs which were difficult to synthesize in the past;2)a series of macrocycles with completely different properties and structures can be explored by modifying pillar[5]arenes;3)pillararenes tend to form five-membered rings that are not common in nature during the cyclization process.In Chapter 2,the partial oxidized and per-oxidized products of pillar[5]arenes were summarized,including their synthesis,structural properties and further derivatization.Pillar[4]arene[1]quinone,one of the partial oxidized products,has played a important role in the development of new macrocycles due to the introduced benzoquinone unit.The purpose of the experiment is to further modify the pillar[4]arene[1]quinone and obtain a novel macrocycle;the experimental method is implementing Diels-Alder reaction on it with 1,3-butadiene,isolate the main product and complete structural characterization;experimental results display that the double bond on the benzoquinone unit of the starting material would selectively react with the unilateral addition reaction of the quinone unit,the results of X-ray crystal diffraction show that the modified new macrocyclic molecule DA-1 The rigid pentagonal pillar structure cannot be maintained.A benzene ring unit adjacent to the modified quinone unit displaying horizontal state,at the same time,the solvent can also affect the conformation and provide the driving force for conformational conversion: acetonitrile molecules can enter the cavity and push the horizontal units out,this conversion process can also be proved by NMR spectra with different deuterated solvents.It can be concluded that a novel macrocycle was synthesized and originally rigid pentagonal pillar structure and the original symmetry were destroyed,exhibiting a completely different conformation.In Chapter 3,a new class of macrocycles derived from rim-differentiated pillar[5]arenes—tiara[5]arenes were introduced initially,including design strategies,synthesis,structures and related properties.Three novel macrocycles are derivatives of tiara[5]arenes modified by the Suzuki-Miyaura cross coupling.The purpose of the experiment is modifying the tiara[5]arene by forming a carbon-carbon single bond;the method is that three different phenylboronic acids reacted with the tiara[5]arene;the experimental results display that the three derivatives have been successfully synthesized.The compounds were identified by NMR and mass spectroscopy;it was concluded that a new macrocyclic body was developed based on the tiara[5]arene,this derivation added a “second-layer structure” on the tiara[5]arene,endowing higher flexibility and can provide potential building blocks for further complex 3D structures.Finally,a summary and outlook on the newly synthesized molecules was introduced.Tiara[5]arene derivatives will play an important role in supramolecular chemistry due to the fivefold symmetric axis,providing a potential building block for building metalorganic or covalent organic molecular polyhedra.At the same time,the second-layer structure of tiara[5]arene increases the flexibility of the macrocycle,which increases the flexibility and possibilities to acquire the segments of nanotube or the construction of complex 3D structures.更多还原