刚性不对称氟硼配合物的合成及光物理性质研究

项目名称： 刚性不对称氟硼配合物的合成及光物理性质研究

项目编号： No.21471042

项目类型： 面上项目

立项/批准年度： 2015

项目学科： 数理科学和化学

项目作者： 卢华

作者单位： 杭州师范大学

项目金额： 80万元

中文摘要： BODIPY是一类十分重要的新型荧光材料，但对称性的结构使其易于紧密堆积和具有较小的Stokes位移，因而在固态下荧光淬灭。本项目拟通过母核扩展修饰，meso-位取代基的拓展，外围共轭，顺反异构等方法构建一系列具有有效固体发光的刚性结构的不对称新型氟硼配合物。对这些配合物在不同溶剂和固态下（薄膜，粉末，晶体）的光物理性质如紫外光谱、荧光光谱、荧光寿命、（绝对）量子产率、辐射速率以及非辐射速率等进行详细研究。结合量子化学理论计算和电化学数据，研究母核修饰，meso-位取代基，外围共轭以及顺反异构对轨道能量和光物理性质的影响，分析分子间的相互作用及聚集状态与固体发光效率之间的关系，为进一步的新型氟硼配合物分子材料的设计提供数据支持和理论指导。通过对光物理性质和轨道能量的详细研究，筛选出可应用于固态荧光传感器和发光器件的新型发光材料。

中文关键词： BODIPY；光物理性质；DFT计算；氟硼配合物；构效关系

英文摘要： Boradiazaindacenes (BODIPY) are a well-known and important type of novel fluorescent materials. However, the solid-state emission properties of most BODIPY derivatives have been found to be poor because of the strong intermolecular interactions and the small Stokes shifts that probably result from it's symmetric structure. Herein, a serial of asymmetric and rigid difluoroboron complexs with effective solid-state emission are designed using a facile synthetic method through core extension, meso-subsituent, peripheral conjugated and syn-anti isomerization. The photophysical properties such as absorption and emission spectra, fluorescence lifetime, (absolute) fluorescence quantum yield, radiative and nonradiative decay of the compounds in kinds of solvents and solid-state will be investigated in detail. The behavior of photophysical properties and orbital energy of the complexs in various structural modification strategies will be analyzed, the relationship between intermolecular interaction or aggregation state and the solid-state emission efficiency will be researched in order to explore the structure-property relationships， this should facilitate the future rational design of BODIPY analogues with properties suitable for specific practical applications. Some complexs, have potential application in solid-state fluorescent sensor or optoelectronic device, should be selected through this research.

英文关键词： BODIPY;Photophysical properties;DFT calculation;Fluoroboron complexs;Relationship of structure/property