新型七元环N,N硼络合物可见/近红外共轭荧光染料的合成及性能研究

Organic boron complexes have attracted extensive attention because they have the novel molecular structures and good photoelectric properties, so it is of great scientific significance to design boron complex fluorescent dyes with superior liquid and solid state luminescence properties. On the basis of the current domestic and international research status and preliminary exploration, through reasonable design, to synthesize novel seven-membered ring N,N boron complex visible/near-infrared dyes that have high fluorescent quantum yield in liquid and solid. We will plan to carry out the work from the following three aspects: (one) to design and synthesis of the seven-membered ring N,N boron complex matrix molecule, at the same time, to modify the periphery of the molecular matrix by using aromatic groups, and thus we will get new fluorescent molecules with novel molecular structures and excellent luminescence properties in solid state; (two) to design and synthesize furan- or thiophene-fused seven-membered ring N,N boron complexes, by extending the molecular conjugated length, realizing the transition of the emission bands of the molecules from the visible to the near-infrared region, so we will build the visible/near infrared fluorescent molecules with tunable fluorescent emission; (three) to design and synthesize the molecular skeleton containing two seven-membered ring N,N boron complex parent molecules which were fused together, and through a significant extension of molecular skeleton π-conjugated length, building near-infrared fluorescent molecules with large molar extinction coefficient and high solution state and solid state fluorescence quantum yield.

有机硼络合物由于具有新颖的分子结构和良好的光电性质而受到广泛关注，设计具有优异溶液态和固态发光性能的硼络合物荧光染料具有重要的科学意义。本项目在目前国内外研究现状和前期探索的基础上，通过合理设计，合成具有高的溶液态和固态荧光量子产率的新型七元环N,N硼络合物可见/近红外荧光染料，拟从以下三个方面展开工作：（一）设计合成七元环N,N硼络合物分子母体，同时利用芳香基团对分子母体进行外围修饰，得到具有新颖分子结构和优异的固态发光性能的新型荧光分子；（二）设计合成呋喃和噻吩并环七元环N,N硼络合物，通过延长分子π-共轭长度，实现分子的发射谱带从可见区到近红外区的跨入，构筑荧光可调的可见/近红外荧光分子；（三）设计合成双七元环N,N硼络合物母体稠并的分子骨架，通过分子骨架π-共轭长度的显著延长，构筑具有大的摩尔消光系数和高的溶液态及固态荧光量子产率的近红外荧光分子。

由于其新颖的分子结构和良好的光电性质，有机硼络合物受到了广泛关注，在光电材料领域表现出极大的应用前景，设计具有优异溶液态/固态发光性能的硼络合物荧光染料具有重要的理论意义和实际应用价值。本项目在目前国内外研究现状和前期探索的基础上，通过合理设计，合成具有高的溶液态/固态发光效率的新型七元环N,N硼络合物可见/近红外荧光染料，并对其光物理性能进行了研究。取得了以下研究成果：（一）设计合成含有取代苯的基于苯并噻唑/噁唑的单七元环N,N硼络合物，通过在染料母体外围的适当修饰，得到荧光可调的AIE/AIEE型高固态发光的染料分子，其固态发光效率效率多数高于0.60，在固态激光、发光器件等方面有着重要的应用；（二）设计合成含有四苯乙烯、咔唑、三苯胺等大π-共轭芳香基团的基于苯并噻唑/噁唑的单七元环N,N硼络合物，通过在染料母体外围的修饰，得到荧光可调的高固态发光效率的可见/近红外的染料分子；（三）设计合成双七元环N,N 硼络合物母体稠并的分子骨架，得到具有高的溶液态和固态荧光光量子产率的近红外荧光分子。该类分子具有大的摩尔消光系数和高的溶液态/固态荧光量子产率的近红外荧光分子；（四）设计合成了四苯乙烯或四苯基丁二烯功能化的β-二酮硼和β-酮亚胺氟硼络合物，并研究了这些有机硼络合物荧光染料的ICT、AIE和力致荧光变色性质。