基于硼氮萘电子砌块反应活性探究构筑硼氮功能分子及其性能研究

The synthesis and evaluation of BN isosteres of archetypical aromatic hydrocarbons has been a fruitful and active area of research in main group and organic materials chemistry in the past few years. The substitution of a C=C double bond with the more polarized B-N unit within a larger aromatic framework can have beneficial effects on the packing, absorption and electron transporting properties of the molecules and materials compared to the all carbon frameworks. Nevertheless, the synthetic strategies are still quite limited and they usually rely on classical electrophilic borylations performed under harsh conditions. Therefore, in this project, the keystone reactions such as the hydrosilylation, cross-dehydrogetative couplings amination and cyclization strategy have been investigated to construct BN-aromatic systems. On the other hand, the effects that the replacement of a C=C bond by a B−N bond have on the properties of BN-aromatic compounds are still not fully understood, and therefore, they are not always easy to predict. In this project, the development of new synthetic methodologies for the preparation of novel BN-aromatic compounds would enable a more systematic study of their structure−property relationships and ultimately trigger the rational design of novel BN-polycyclic aromatics with improved properties, the chemical and phsical properties of these molecules will be extensively studied experimentally and theoretically.

有机硼氮共轭分子的构筑和性能研究一直是主族元素有机化学研究的前沿领域。然而，受限于缺乏高效的合成方法，目前硼氮芳香化合物的种类和数量还较少，极大地限制了人们对这类新结构性质和功能的深入了解。本项目拟以硼氮萘为研究模型，利用C-H原位功能化反应，结合理论计算，开辟硼氮芳香化合物3种全新反应模式，探索反应规律，分析硼氮芳香化合物与传统芳烃化合物反应性质产生差异的原因，揭示硼氮杂分子丰富的化学性质和独特的结构特征及物理特性，为新型硼氮分子的设计合成提供重要的基础数据。通过原位功能化反应和增环反应策略，设计并合成几类结构新颖的硼氮稠环化合物。研究其分子结构变化与其光电性能的相关性规律，揭示BN单元的嵌入对有机共轭材料光电性能影响的机制；阐述硼氮功能化合物的设计原则，为新型有机光电材料的设计和开发提供理论依据。本项目的实施将推进含硼有机光电材料的更深层次发展，为新型硼氮功能材料的设计注入新的活力。

本项目以结构简单且极具代表性的1,2-硼氮萘为研究对象，对其未知反应类型进行了探索。在此基础上，设计合成系列含有B-N单元的新型稠环化合物，通过结构表征与性能测试，建立了结构与性能的构效关系。同时通过应用探索，实现了硼氮稠环化合物指纹高清识别、信息防伪、癌细胞亚细胞器精准定位、炸药可视化检测等应用研究。阐述了硼氮单元在调控稠环化合物反应性质及光电功能方面的作用。目前研究结果充分展现了硼氮稠环化合物在构筑新结构实现新功能方面的巨大潜力。