新型BODIPY-茚酮类近红外荧光染料的合成与光物理性质研究

In this project, a series of NIR fluorescent BODIPY derivatives were synthesized based on the condensation and ring close between BODIPY and indandione. With the introducing of electron-donor and electron-acceptor groups to the target molecular structure, the emission maxima red-shifted by tunning the intramolecular electron distribution.Totaly four series of target molecules were estabalished: 1) compounds obtained by condensation between the aldehyde and indandione; 2) ring closed between methyl of 3-substitued in BODIPY and carbon atom of carbonyl of indandione. Strengthed molecular structure facilitates for the increase of fluorescent quantum yield; 3) a series of symmetry and asymmetry ring closed BODIPY-indandione derivatives; 4) compounds of fluorine atoms substitued by aromatic system in the target molecules mentioned above. Optimizing and establishing the molecular structures of fluorescent dyes with high quantum yield and near infrared emission(NIE).Based on experimental results, find the compounds with high quantum yield, near infrared emission, photo-senstive,and photostability.Quantum calculation for the designed molecules were carried out based on the platform of Material Studio.Investigaing the structure-property relationship and uncovering the prinples hiden in it.Together with the results obtained from quantum calculation, a reasonable explanation for the structure-property relationship will be given.

本项目旨在设计合成一系列基于BODIPY与茚酮类化合物缩合与成环的新型近红外发射的BODIPY衍生物。通过推拉电子基团的引入来调节分子内电荷的分布以实现BODIPY母体发射波长的红移。分子设计分四个系列：1)BODIPY分子中的醛基与茚酮类化合物缩合后的产物；2)BODIPY3-位的甲基与茚酮的羰基反应而成环的产物，刚性的分子骨架有利于荧光量子效率的提高；3)对称与不对称的BODIPY-茚酮衍生物的合成；4)以芳香体系取代前三个系列的BODIPY衍生物中的氟原子，优化并构建高荧光量子效率，近红外发射的荧光染料。通过实验测试遴选发光效率高、近红外发射、光敏性高、光稳定性好的化合物。对所设计的分子在Material Studio软件平台上进行量子计算。探索这类化合物结构与物理性质之间的规律性。结合分子模拟计算结果解释其中的规律性。

荧光染料的持续迅猛发展得益于科学工作者们在生物、化学、材料领域的广泛应用。氟硼荧光染料经化学修饰已经极大的提高了染料的光化学稳定性，而且具有较高的摩尔吸光系数和荧光量子效率。BODIPY是氟硼荧光染料的典型代表。本项目通过BODIPY与茚酮的缩合并在分子内构建刚性的七圆环的系列氟硼荧光染料，完成结构表征。通过化学修饰来调控分子的发射波长，构建高效发光的氟硼荧光染料。项目设计主要包含以下几个方面的研究工作1) BODIPY与1,3-茚二酮和3-(二氰基甲基)茚-1-酮的缩合产物及其性质研究；2) 缩合产物分子内成环构建七圆环，分子恢复刚性同时发射波长红移至黄光区域；3) 通过Sonogashira偶联反应扩展分子共轭体系，调控分子的发射波长；4) 在BODIPY分子两侧构建对称的含茚的刚性七圆环衍生物,发射波长同时红移至630nm；5) BOPHY与3-(二氰基甲基)茚-1-酮的缩合构建分子内七圆环衍生物，研究类似BODIPY产物在缩合与成环反应及其光谱性质；6) BODIPY与苯乙酮的羟醛缩合反应研究。在BODIPY与3-(二氰基甲基)茚-1-酮的缩合成环产物中引入萘酰亚胺大共轭基团及其对发射波长的影响；在成环产物的甲基处缩合硫杂冠醚，构建了一个Hg2+荧光化学传感器。在MaterialsStudio计算平台上对合成了分子进行分子结构的优化模拟，探索化合结构与性质之间的规律。通过项目的研究，建立起了一套具有新型氟硼染料结构体系的荧光染料。