基于桥环结构的新型氟硼吡咯类近红外荧光分子的创制与性能研究

The near infrared(NIR) fluorescent molecule which has an extensive applied foreground in the field of molecular fluorescent probes, photodynamic therapy therapy, OLED, and so on has received great attention . Researched the inner connections between the structure and performance of the molecule and established the relationship in the structure and property at the molecular level, and to establish the feasible theory model for designing the molecule which was the key for the breakthrough progress in this field. The research target of this project.was the Boron Pyrromethene compounds with the rigid structure of the ring bridge, and the main job was designed and synthesized the molecule which has the long emission wavelength, high fluorescent quantum efficiency and good fluorescent performance. Bringing the ring structures in the bridge can improve the rigid of the fluorescent molecules and amplify the big π conjugate system, The near infrared fluorescent molecule of Boron Pyrromethene which has potential application value will be designed and synthesized through the research of the.ring bridge, the effect of substituents, intra-molecular D-A system function and fluorine boron complexation. Develop the green synthetic route of the typical structures, expands synthetic methods and techniques in the green chemistry studied on the relationship between the structure and performance of the fluorescent material, establish the theory model for designing the molecule. Screened out the fluorescent molecule with good fluorescence performance and exploited its application, and to get some certain practical application value molecules in near infrared fluorescent material. At last, provide certain theoretical basis for the development and utilization of near infrared fluorescent molecules.

近红外荧光分子由于其在荧光探针、分子光动力学疗法(PDT)、OLED等领域的应用前景受到了极大的关注。研究结构与性能间的内在规律性联系，并从分子层面上建立构效关系，从而建立可行的分子设计理论模型是该研究领域取得突破性进展的关键。本项目以具有刚性结构的桥环氟硼吡咯分子为研究目标，分子设计并合成具有长发射波长、高荧光量子效率和荧光性能的分子。通过在氟硼类化合物的桥上引入环状结构提高母体分子的刚性和大π共轭体系，并通过取代基效应、分子内D-A体系作用及氟硼络合作用设计合成具有潜在应用价值的近红外荧光分子。研究典型结构的绿色合成，拓展绿色合成方法和技术。研究分子结构与性能之间的关系，探索建立该类材料分子的设计模型。筛选出具有优良荧光性能的分子，研究其实际应用的可能性，得到有一定实际应用价值的分子，为近红外荧光分子的开发利用提供一定的理论基础和实际应用价值。

本项目开发了碘促进以及二价铜促进的环合/氧化芳构化方法，构建C-N键，进而合成稠氮杂环化合物共七大类，其中发展了多取代吡咯、醌并吡咯、咪唑等杂环的简单高效的合成方法。在荧光小分子的开发上面，以香豆素和醌结构为主体，合成了15个系列的荧光分子，并在溶液荧光、固体荧光、取代基、溶剂探针、pH探针、离子探针等方面开发了具有大的大的斯托克斯位移、高荧光量子产率得荧光分子。