新型稠杂环芳烃的合成及其光电性能研究

For the advantages of structure diversity, easily processing, inexpensive, eco-friendly, easily preparation of flexible portable device, organic semiconductor material has caught worldwide attention of academic and industrial in recent years. This project is expected to carry out the study of the synthesis of novel polyheterocyclic aromatic hydrocarbons by the intermolecular condensation of isoflavone or 3-halochromone with hydrazine, aminoazoles, etal. and intra-molecular condensatio by photochemistry. The electrochemical properties and heat stability of material properties of polyheterocyclic aromatic hydrocarbons are investigated by experiment. The organic optoelectronic devices of polyheterocyclic aromatic hydrocarbons are prepared and its performance are tested. The key reaction of synthesis novel polyheterocyclic aromatic hydrocarbons is closed ring step by photochemistry reaction. It is not need any reagent and the byproducts is only water in the step by photochemistry.The solubility of desigined polyheterocyclic aromatic hydrocarbons in the project are improved by the changing of substitut gruop and keeping indentations in the molecules, it is benefit to machine OFETs device and OLEDs. The introduction of bigger electricity negative N, S, O atoms than C to aromatic ring of polyheterocyclic aromatic hydrocarbons, can enhance the capacity of the electronic injection and transmission for organic material, it is helpful to explore the relationship between the structure of polyheterocyclic aromatic hydrocarbons and performance of semiconductor materials. Pave the way for the development of the N type semiconductor materials with stable performance, excellent, and easily processing.

有机OFETs器件或OLEDs器件近年来引起了学术界和产业界广泛关注。本项目分别以异黄酮和3-芳基色元酮为原料与肼、脒、氨基唑进行分子间缩合，再通过光化学反应进行分子内的脱水关环合成稠杂环芳烃，并对稠杂环芳烃的材料学性质和器件的光电性能进行研究。利用光化学反应实现稠杂环芳烃合成的关键步骤--关环反应，不需要其它反应试剂并且副产物是水。设计合成的稠杂环芳烃，通过改变取代基或在有些分子结构中预留缺口，改善溶解性能，易于有机光电器件的加工。电负性比碳大的氮原子的引入，使嘧啶并稠环芳烃具有良好的n-型有机半导体性能；π键共轭体系的增大有利于稠杂环芳烃电致发光性能的改善；噻吩并含氮稠环芳烃具有电子传输和发光双功能。通过合成路线短、反应绿色化的失水缩合反应合成结构新颖、类型丰富的含N和S杂原子稠环芳烃，有利于发现稠环芳烃结构的变化对器件性能调控作用的规律，为开发性能优良的有机光电器件奠定基础。

本项目以异黄酮、3-(1-萘基)色原酮和3-(9-菲基)色原酮类化合物分别与肼、苯肼、胍、脒、3-氨基吡唑、3-氨基-1,2,4-三氮唑等进行缩合反应，得到邻二芳基吡唑及邻二芳基嘧啶等中间体，合成的中间体再在乙醇溶液中采用紫外光照射，可以直接实现分子内光环化脱水反应，合成共轭体系大且结构新颖的2H-二苯并[e,g]吲唑、1-苯基二苯并[e,g]吲唑、吡唑并[1,5-f]菲啶、二苯并[f,h][1,2,4]三唑并[3,4-b]喹唑啉、二苯并[f,h]喹唑啉、苯并[h]-萘并[1,2-f]喹唑啉、苯并[h]-菲并[9,10-f]喹唑啉、2H-屈并[5,6-c]吡唑和7a-苯基苯并吡喃并[2,3-b]氮丙啶-7-酮等9类环系的稠杂环化合物150种，建立了合成新型含吡唑、嘧啶芳香稠杂环化合物的新方法。发现了邻2-羟基苯基、芳基杂环化合物的芳基类型和杂环化合物类型与分子内脱水光照关环反应活性的规律。本项目建立的光环化反应合成芳香稠杂环化合物为分子内缩合反应，反应副产物为水、原子利用率高，反应条件温和，合成步骤简捷，是典型的绿色反应。通过对所合成的稠杂环化合物进行荧光性质研究，发现了2H-二苯并[e,g]吲唑，二苯并[f,h][1,2,4]三唑并[3,4-b]喹唑啉、2H-屈[5,6-c]吡唑和2H-屈[5,6-c]吡唑-13-醇化合物具有良好的荧光性能，为这些杂环化合物在有机光电材料开发中的应用奠定了基础。该项目在RSC Advances，Synthesis，Molecular Diversity等期刊发表研究论文11篇，申请发明专利2项，培养博士研究生2人、硕士研究生5人。