芘并硼氮杂菲的合成、结构及光物理性质研究  

Study on the Synthesis,Structure and Photophysical Properties of Pyrene Fused BN-embedded Phenanthrene

作　　者：郝玉银 蒋震 刘志强[1] HAO Yuyin;JIANG Zhen;LIU Zhiqiang(Institute of Crystal Materials,Shandong University,Jinan 250100,China)

机构地区：[1]山东大学晶体材料研究院,山东济南250100

出　　处：《合成化学》2024年第11期992-999,共8页Chinese Journal of Synthetic Chemistry

基　　金：国家自然科学基金-NSAF基金资助项目(U2330106)。

摘　　要：近年来,硼氮杂稠环芳烃在有机光电功能材料领域展现出巨大潜力,但是对于具有大共轭结构的硼氮杂稠环芳烃的合成与性质研究仍然有待深入。本文报道了基于胺基前体硼化反应路线合成2个芘并硼氮杂菲化合物并开展的光物理性质研究,合成路线简单,一锅反应最多同时新形成4个化学键。研究表明:1-BN-2-Na-Py和2-BN-1-Na-Py具有高荧光量子产率(0.46,0.70)和双光子吸收截面(230 GM以上)。X-射线单晶衍射解析了2-BN-1-Na-Py的单晶结构,表明2-BN-1-Na-Py分子优良的平面性,确证了B—N键具有部分双键特征。通过密度泛函理论(DFT)计算表明:硼嗪单元(BNC4环)具有一定的芳香性(NICS(1)值为-4.923,-1.935),解释了B—N键的引入对化合物电子结构的影响。In recent years,boron nitrogen heterocyclic aromatic hydrocarbons have shown great potential in the field of organic optoelectronic functional materials,but the synthesis and properties of boron nitrogen heterocyclic aromatic hydrocarbons with large conjugated structures still need further research.This article reports the synthesis of two pyrene fused BN-embedded phenanthrene compounds based on the amine precursor boronation reaction route and the study of their photophysical properties.The synthesis route is simple,with up to four new chemical bonds formed simultaneously in one pot reaction.Experiments have shown that photophysical data shows that 1-BN-2-Na-Py and 2-BN-1-Na-Py have high fluorescence quantum yields(0.46,0.70)and two-photon absorption cross-sections(above 230 GM).The single crystal structure of 2-BN-1-Na-Py was analyzed by X-ray single crystal diffraction,indicating excellent planarity of the 2-BN-1-Na-Py molecule,and confirming that the B-N bond has some double bond characteristics.Density functional theory(DFT)calculations have shown that the borozine unit(BNC4 ring)has a certain degree of aromaticity(NICS(1)values of-4.923 and-1.935),explaining the effect of the introduction of B—N bonds on the electronic structure of the compound.

关 键 词：硼嗪 硼氮杂菲 多环芳烃 单晶结构 亲电硼化 

分 类 号：O621.3[理学—有机化学]