基于芳基乙炔结构的稠环芳香大分子的设计合成及性质研究

项目名称： 基于芳基乙炔结构的稠环芳香大分子的设计合成及性质研究

项目编号： No.51473003

项目类型： 面上项目

立项/批准年度： 2015

项目学科： 一般工业技术

项目作者： 赵达慧

作者单位： 北京大学

项目金额： 85万元

中文摘要： 从有机小分子出发，自下而上、结构可控地制备具有石墨烯片段结构特征的大型稠环芳香分子是有机光电材料领域的重要研究课题。本项目选择以芳基取代的末端乙炔作为关键的中间体结构，来进行相关材料的设计合成。这一合成策略的主要优势在于，由于末端炔烃本身的空间位阻小，对与其发生反应的化合物的空阻容忍性较高。例如，它可与有较大空阻的卤代芳烃进行高效的偶联反应。利用这些结构及反应特点，我们就可以运用聚合反应来一步构建巨大的碳骨架结构。接下来，通过探索和优化对炔基三键的加成-关环、环加成等后修饰反应，实现聚合物中多位点的sp杂化的炔基向sp2碳的芳烃片段的转化。进而经过分子内氧化偶联反应的筛选和条件优化，实现大尺寸的稠环芳香结构的合成。此外，摸索掌握所合成的稠环芳香分子和材料的表征方法，研究其分子聚集特性，考察单分子及凝聚态下材料的半导体、光学、传感等方面的性质，探索其功能性应用，也是本项目的重要研究内容。

中文关键词： 稠环化合物；共轭聚合物；设计与合成；石墨烯；有机半导体

英文摘要： Using small organic molecules as starting materials to synthesize large pi-conjugated polycyclic aromatic molecules, which are fragmental structures of graphene, from the bottom-up approach is a very important topic in the field of organic opto-electronics. In this project, we design to harness aryl-substituted terminal ethynylene as the key building block and intermediate structure to accomplish the syntheses of relevant materials. The main advantage of this strategy is that, due to its slim geometry, terminal ethynylene is quite tolerant of the steric bulkiness of its reacting partners. For example, Pd-catalyzed Sonogashira cross coupling can be achieved with high efficiency between a terminal alkyne and a sterically highly hindered aryl halide. Taking advantage of the unique structure and potent reactivity of aryl alkyne, we now apply polymerization reactions to the syntheses of particularly large polycyclic aromatic molecules, as polymerization process can realize the extension and expansion of carbon skeletons in one step with the highest efficiency. Subsequently, the ethynylene units in these aromatic polymers will be transformed into sp2 aromatic carbons via post-polymerization modifications, such as electrophilic addition/annulation tandem reaction and cyclo-addition with proper diene groups. Upon the following intramolecular oxidative coupling, these highly substituted macromolecules will then be converted into large, planar conjugated polycyclic aomatics and partial graphene structures. Further studies will involve characterizations of the synthesized macromolecules and materials, including the aggregation and assembly behaviors, semiconducting, optical, and sensing properties, and so on.

英文关键词： polycyclic aromatic compound;conjugated polymer;design and synthesis;graphene;organic semiconductor