嘧啶类硼氟荧光分子的构建及其性质研究

发布时间：2018-07-06 08:00

本文选题：BODIPY + 斯托克斯位移　；参考：《聊城大学》2017年硕士论文

【摘要】：硼氟二吡咯(BODIPY)作为一类经典的有机硼氟化合物,因其优良的光物理性质而为人们所熟知。这类化合物具有较高的摩尔吸收系数和荧光量子产率以及波长可调等优点,被广泛应用于荧光探针和成像、光捕获系统等领域。但是经典BODIPY荧光斯托克斯位移较小(7-15 nm),分子自吸收严重。另外,聚集诱导荧光猝灭的特性导致BODIPY荧光分子在固态聚集条件下几乎不发光。因此,近些年来化学家们则致力于设计合成具有大Stokes位移和高效固态发光的BODIPY类荧光分子。为了实现这一目标,本论文以嘧啶为核心设计合成一系列具有大Stokes位移和高效固态发光的新型硼氟荧光分子。对所得到的分子进行光谱性质分析、单晶结构解析并结合理论计算对其发光性能之间的内在关联进行了详细研究。内容主要包括以下几个部分:1.首先采用N^N不对称双齿配体策略,通过2-吡啶乙腈与4,6-二氯嘧啶的共轭,合成了嘧啶-吡啶类硼氟荧光分子1-8。该类化合物不仅在溶液中具有优良的发光性能(0.13-0.90),在固态粉末状态也表现出中等的荧光量子产率(0.18-0.36)。发射波长能够通过不同官能团的修饰进行调控,并且波长的移动范围还可以通过理论计算进行预测。研究结果表明,通过N^N不对称双齿配体策合成的荧光分子,能够改善经典BODIPY聚集诱导荧光猝灭的特性,但是若想应用于固体发光材料,化合物的荧光量子产率还需进一步提高。另外,化合物4、5和7表现出可逆的较为灵敏的压敏响应荧光性能。这种合成路线短、结构修饰简单易行、溶液中及固态粉末条件下均具有良好光物理性能的化合物,有望进一步应用到压敏等智能材料领域。2.为了得到高效固态发光的荧光分子,本文第三章内容在N^O不对称的基础上结合AIE策略设计合成了嘧啶-烯酮类的荧光分子9-12。该系列化合物表现出AIE效应、波长可调、大Stokes位移以及高固态荧光量子产率。另外,化合物12还表现出可逆的压力刺激响应行为,化合物12的固态粉末自然状态下结构堆积较为松散,若给予一定的压力进行研磨,分子结构的平面性能增加,π共轭程度得到延伸,促进ICT效应增强,发射波长红移。这类有高固态量子产率和对压力刺激敏感的化合物具有应用到荧光智能材料等领域的潜力。3.由于双核硼荧光分子的π共轭程度远大于单核硼荧光分子,在光电子器件等领域具有更大的应用潜力。本文第四章内容将嘧啶上的两个氯原子均用2-苯基苯乙酮取代,合成BF2和BPh2络合的双核硼荧光分子13-15。固态粉末条件下化合物13-15的荧光量子产率分别为0.12,035,0.18。由于苯环数量的增加,导致该系列化合物在溶液中也具有适中的荧光量子产率。化合物13-15与单核硼分子9-12相比吸收和发射波长发生明显红移,其中发射波长红移至远红光区域。该类分子在溶液以及固体条件下的荧光发射,使其有望进一步应用于荧光成像及固态发光材料等领域。
[Abstract]:Borofluorine two pyrrole (BODIPY), as a class of classical organic borofluorine compounds, is well known for its excellent photophysical properties. These compounds have the advantages of high molar absorption coefficient, fluorescence quantum yield and wavelength tunability, and are widely used in the fields of fluorescence probe and imaging, optical capture system and so on. But classic BODIPY The fluorescence Stokes shift is smaller (7-15 nm), and the molecular self absorption is serious. In addition, the characteristics of the fluorescence quenching induced by aggregation lead to the almost non luminescence of the BODIPY fluorescent molecules under the solid-state aggregation condition. Therefore, in recent years, chemists have been devotes to the design and synthesis of BODIPY type fluorescent molecules with large s tokes displacement and high efficiency solid state luminescence. In this paper, a series of new boron fluorofluorescence molecules with large s tokes displacement and high efficiency solid state luminescence are designed and synthesized with pyrimidine as the core. The spectral properties of the obtained molecules are analyzed. The crystal structure analysis and theoretical calculation are used to study the correlation between the luminescence properties. The following parts: 1. first, using the N^N asymmetric ditoothed ligand strategy, the pyrimidine pyridine pyridine fluorofluorescence molecule 1-8. is synthesized by the conjugation of 2- pyridine acetonitrile and 4,6- chlorouracil, which not only has excellent luminescence properties (0.13-0.90) in the solution, but also shows a medium fluorescence quantum yield (0.18-0) in the state of solid powder (0.18-0). .36). The emission wavelengths can be regulated by the modification of different functional groups, and the range of the wavelength can be predicted by theoretical calculation. The results show that the fluorescence molecules synthesized by the asymmetric biolant ligand of N^N can improve the characteristics of the fluorescence quenching of the classical BODIPY aggregation, but if they want to be applied to solid luminescence The fluorescence quantum yields of the materials and compounds need to be further improved. In addition, the compounds 4,5 and 7 show a reversible and sensitive pressure sensitive response fluorescence. The synthetic route is short, the structural modification is easy and the compound with good light rational energy in both the solution and the solid powder condition is expected to be further applied to the pressure sensitive intelligence. .2. in order to obtain high efficiency solid luminescent molecules in the field of energy materials, the third chapter of this article is to design and synthesize the pyrimidine - allenone fluorescent molecule 9-12. on the basis of N^O asymmetry and the AIE strategy. The series of compounds show the AIE effect, the wavelength is adjustable, the large s tokes displacement and the high solid fluorescence quantum yield. In addition, compound 12 also It shows a reversible pressure stimulus response, and the structure of the compound 12 is loosely packed in the natural state of the powder. If a certain pressure is grind, the plane properties of the molecular structure are increased, the degree of pi conjugation is extended, the ICT effect is enhanced and the emission wavelength is red shift. This kind of high solid quantum yield and pressure irritation sensitivity The potential compounds have the potential to be applied to the field of fluorescent intelligent materials.3. because the conjugated degree of the biuclear boron fluorescent molecules is far greater than that of the mononuclear boron fluorescent molecules, and has a greater potential for application in the fields of optoelectronic devices. In the fourth chapter, the two chlorine atoms on pyrimidine were substituted by 2- phenyl acetophenone to synthesize BF2 and BPh2 collaterals. The fluorescence quantum yield of compound 13-15 with 13-15. solid powder is 0.12035,0.18. because of the increase of the number of benzene ring, which leads to the moderate fluorescence quantum yield in the solution. Compound 13-15 and mononuclear boron molecule 9-12 phase absorption and emission wavelength obviously red shift, The medium emission wavelength is red to the far red region. The fluorescence emission of these molecules in solution and solid conditions is expected to be further applied to the fields of fluorescence imaging and solid-state luminescence.
【学位授予单位】：聊城大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O657.3

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