新型二吡咯化合物的合成及光学性质研究

发布时间：2018-05-03 21:20

本文选题：氟硼二吡咯甲川类化合物 + 手性　；参考：《北京科技大学》2017年博士论文

【摘要】：近年来,有机发光材料作为一种重要研究工具因其优异的表现而被全世界众多科学家所认可,从而得到了十分快速的发展。与无机发光材料相比,有机发光材料拥有在可见光区域内较高的摩尔消光系数、易于修饰和种类繁多等优势,被广泛应用于多个领域,如化学分析、太阳能转化、有机发光二极管(OLED)等。因此开发利用具有优良性质的有机发光分子已成为当前倍受关注的研究课题。氟硼二吡咯甲川类(Bodipy)化合物迷人的结构赋予了它们很多独特的性能,并且,Bodipy类化合物是比较容易被修饰的,Bodipy骨架周边几乎所有的位置都可以被修饰,使Bodipy类化合物具有不同的性质,以达到不同的应用目的。但是,Bodipy类化合物在实际应用中也存在着一定的局限性,例如,化合物的吸收一般局限在470-530 nm,并且较小斯托克斯位移(Stokes shift)使化合物在浓溶液中存在明显的自吸收现象而使其荧光强度减弱,在固态中存在聚集诱导的荧光淬灭现象(ACQ)等。这些问题大大限制了这类化合物的应用,因此设计和合成能够改善这些问题的新型Bodipy类化合物,成为了近年来的研究重点。本论文主要针对在Bodipy类化合物在实际应用中存在的不同问题,设计合成了三类新型的Bodipy类化合物,具体内容如下:(1)合成了两个手性苯并氮杂Bodipy化合物,分别是一个1,1-联二萘酚取代的苯并氮杂Bodipy和两个1,1-联二萘酚取代的苯并氮杂Bodipy,并对它们的谱学性质进行了研究。通过在Bodipy的周边共轭上苯环,同时在其周边引入手性联二萘取代基团,得到的苯并氮杂Bodipy在近红外区域有了光学活性。于是我们合成了第一例在近红外区域有光学活性的手性Bodipy。为了对比研究,我们还合成了一个没有手性取代基Bodipy作为参照化合物(2)合成了一系列功能化的三芳胺取代的Bodipy类化合物Bodipy-TPA-R(R = BI,BH-OH,BH-COOH)以及参照化合物 Bodipy-TPA。这些功能化的Bodipy化合物在溶液中表现出了相类似的光学性质,但是由于分子堆积模式和分子间作用力的不同,它们在固态时却表现出了不同的性质。对于化合物Bodipy-TPA和Bodipy-TPA-BH-COOH而言,它们的晶体中Bodipy骨架结构间没有有效的面对面的π-π堆积作用,并且分子内的转动和三芳胺部分与Bodipy骨架部分的电子转移也都得到了有效的抑制,使这两个化合物都表现出了明显的聚集诱导的荧光现象(AIE)和晶体诱导的红色荧光,它们的晶体绝对荧光量子产率(Ω)分别是19.47%和12.30%。然而,对于化合物Bodipy-TPA-BI和Bodipy-TPA-BH-OH而言,在它们的晶体中,虽然三芳胺部分与Bodipy骨架部分的分子内转动也同样得到了有效的抑制,但是由于两个平行的Bodipy骨架之间存在部分重叠的面对面的π-π堆积作用,它们的晶体绝对荧光量子产率(Ω)是相对较低的,分别是1.37%和3.40%,并且AIE也不明显。另外,对于化合物Bodipy-TPA-BH-COOH,将Bodipy的三芳胺取代基进行功能化的修饰之后,其薄膜荧光在盐酸蒸汽中可以迅速淬灭。(3)通过在Bodipy-TPA的2,6号位置引入不同个数三芳胺取代基得到了化合物Bodipy-2TPA和Bodipy-3TPA。在溶液中,这两个化合物的电子吸收光谱相比于参照化合物Bodipy-TPA仅发生了轻微的红移,但是荧光却发生了明显的红移现象。由于存在激发态的构型弛豫,这两个化合物都拥有较大的斯托克斯位移,分别为约100 nm和约90 nm。同时,由于在Bodipy骨架周围引入了体积较大的三芳胺取代基团,使得这两个化合物的晶体中Bodipy骨架结构间没有有效的面对面的π-π堆积作用,并且分子内的转动和三芳胺部分与Bodipy骨架部分的电子转移也都得到了有效的抑制,使这两个化合物都表现出了明显的聚集诱导的荧光现象(AIE)和晶体诱导的红色荧光,它们的晶体绝对荧光量子产率(Ω)分别是20.54%和13.84%。
[Abstract]:In recent years, as an important research tool, organic light-emitting materials have been recognized by many scientists all over the world because of their excellent performance. Compared with inorganic luminescent materials, organic light-emitting materials have higher molar extinction coefficient in the visible light region, easy to modify and a wide variety of advantages, and so on. It is widely used in many fields, such as chemical analysis, solar energy conversion, organic light-emitting diode (OLED) and so on. Therefore, the development and utilization of organic luminescent molecules with excellent properties has become a popular research topic. The fascinating structure of fluoro boron two pyrrolidine (Bodipy) compounds endows them with a lot of unique properties, and Bodipy The compounds are relatively easy to be modified, and almost all the locations around the Bodipy skeleton can be modified to make Bodipy compounds have different properties to achieve different application purposes. However, there are some limitations in the practical application of Bodipy compounds, for example, the absorption of compounds is generally limited to 470-530 nm, And the smaller Stokes displacement (Stokes shift) makes the compound have obvious self absorption in the concentrated solution and weaken the fluorescence intensity of the compound, and there is an aggregation induced fluorescence quenching phenomenon (ACQ) in the solid state. These problems greatly restrict the application of these compounds, so the design and synthesis of new Bodi can improve these problems. Py compounds have become the focus of research in recent years. In this paper, three new types of Bodipy compounds have been designed and synthesized in the practical application of Bodipy compounds. The specific contents are as follows: (1) two chiral benzo azo heterozygous Bodipy compounds are synthesized, which are substituted by a 1,1- couplet two naphthol, respectively. Nitrogen heterozygous Bodipy and two 1,1- - linked two naphthol substituted benzo - heterozygous Bodipy, and their spectroscopic properties were studied. By introducing the peripheral conjugated benzene ring in the Bodipy, and introducing chiral two naphthalene substituent groups around it, the obtained benzo azo Bodipy was optically active in the near infrared region. So we synthesized the first case In the near infrared region, in order to compare the optically active chiral Bodipy., we also synthesized a series of functionalized three aromatic amine substituted Bodipy compounds Bodipy-TPA-R (R = BI, BH-OH, BH-COOH) as a reference compound (2) and Bodipy, as a reference compound, and the functionalized Bodipy of the reference compound Bodipy-TPA.. The compounds exhibit similar optical properties in the solution, but they exhibit different properties in solid state due to the different molecular stacking modes and intermolecular forces. For the compounds Bodipy-TPA and Bodipy-TPA-BH-COOH, there is no effective face-to-face pion accumulation between the Bodipy skeleton structures in their crystals. The action, the rotation of the intramolecular and the electron transfer of the three arylamine part and the Bodipy skeleton part have been effectively suppressed. The two compounds show obvious aggregation induced fluorescence (AIE) and crystal induced red fluorescence, and their crystal absolute fluorescence quantum yield (omega) is 19.47% and 12.30%., respectively, For the compounds Bodipy-TPA-BI and Bodipy-TPA-BH-OH, in their crystals, although the three arylamine part is also effectively suppressed by the intramolecular rotation of the Bodipy skeleton part, the crystal absolute fluorescence quantum of the two parallel Bodipy skeletons overlaps the face-to-face pion pion accumulation. The yield (omega) is relatively low, 1.37% and 3.40%, respectively, and AIE is not obvious. In addition, after functional modification of the three aryl amine substituents of Bodipy, the film fluorescence can be quenched rapidly in the hydrochloric acid steam for compound Bodipy-TPA-BH-COOH. (3) by introducing a different number of three aryl amines in the 2,6 number of Bodipy-TPA. The compounds Bodipy-2TPA and Bodipy-3TPA. were obtained in the solution. The electron absorption spectra of the two compounds had only a slight red shift compared with the reference compound Bodipy-TPA, but the fluorescence had a significant red shift. The two compounds had a larger Stokes shift because of the configuration relaxation in the excited state. At the same time, about 100 nm and about 90 nm. respectively, due to the introduction of a larger three arylamine substituent group around the Bodipy skeleton, there is no effective face-to-face pion pion accumulation between the crystals of the two compounds, and the intramolecular rotation and the electron transfer of the three arylamine part and the Bodipy skeleton part are also obtained. By effective inhibition, these two compounds show obvious aggregation induced fluorescence phenomena (AIE) and crystal induced red fluorescence. Their crystal absolute fluorescence quantum yields (omega) are 20.54% and 13.84%., respectively.

【学位授予单位】：北京科技大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O626.13;TQ422

【参考文献】