基于吡咯并吡咯二酮的衍生物设计合成及其光学性质的研究
发布时间：2018-08-08 19:32
【摘要】：吡咯并吡咯二酮(DPP)作为有机染料的一种,有着其独特的优势。这是由于DPP是一种有着色泽鲜艳、光稳定性强、耐化学药品、热稳定好、易于合成的高性能的染料。在过去的几年里DPP引起了相当大的研究兴趣。DPP衍生物广泛的被应用在有机太阳能电池(OSCs),场效应晶体管(OFETs),双光子吸收材料,荧光探针等领域。本文设计了六个以DPP为中心的化合物M1到M6,目的是在DPP衍生物在聚集诱导效应和大的双光子吸收截面性能上有一定的突破和进展。首先合成了目标分子M1,M2,M3,通过引入有给电子能力的三苯胺基团和具有强扭曲分子结构的和聚集诱导发光效应的四苯乙烯基团。通过对三种化合物的表征得出,在有机溶剂如四氢呋喃,甲苯,DMF等有良好的溶解性,这也为我们进一步接入端基提供了好的基础。M1,M2,M3在有机溶剂中有很高的荧光量子效率,如在四氢呋喃溶液中荧光量子效率依次为0.94,0.93,0.91。另外,接入四苯乙烯后M3化合物在水含量不断加入到DMF溶剂中表现出了良好的聚集诱导荧光的特点,而M1与M2没有聚集诱导发光的特点,这也表明了通过接入具有AIE效应的基团能够使分子的平面性减弱,分子间相互作用减弱,在纳米聚集态,非辐射衰减减弱,使荧光增强。而四苯乙烯的接入分子平面性减弱,在820 nm波长激发双光子吸收截面化合物M3稍小于M1与M2,但是由于在四苯乙烯引入后,分子共轭体系增大,分子内电荷转移增强,荧光发射红移,在低波段区域(880nm),有很宽的双光子吸收范围,优于化合物M1和M2。然后又以DPP为核心合成了M4,M5,M6化合物。我们选用了比三苯胺的给电子能力更强的二苯胺基团,最后引入具有AIE效应的四苯乙烯基团。通过表征我们得出由于三苯胺的扭曲性比二苯胺好,所以虽然最后引入了四苯乙烯基团,但是M6化合物没有表现出像M3化合物那样的良好的聚集诱导发光效应。这源于二苯胺基团使M6分子平面性优于M3化合物。同化合物M4,M5比较,四苯乙烯的接入使化合物M6淬灭效应减缓,有使分子从ACQ向AIE效应转变的趋势。在双光吸收特点上,M6分子在880 nm波长激发,化合物M6的双光子吸收截面高达618 GM,而M3化合物在这个波长上激发仅有237 GM。
[Abstract]:As a kind of organic dyes, pyrrolidine dione (DPP) has its unique advantages. This is due to the fact that DPP is a high performance dye with bright color, strong light stability, chemical resistance, good thermal stability and easy synthesis. In the past few years, DPP has attracted considerable interest. DPP derivatives have been widely used in the field of (OFETs), two-photon absorption materials, fluorescence probes and so on for (OSCs), field-effect transistors of organic solar cells. In this paper, six compounds M1 to M6 centered on DPP have been designed in order to make a breakthrough and progress in the aggregation induction effect of DPP derivatives and the properties of large two-photon absorption cross sections. Firstly, the target molecule M _ (1) M _ (2) M _ (2) M _ (3) was synthesized by introducing trianiline groups with the ability to give electrons and tetrastyrene groups with strong distorted molecular structure and aggregation induced luminescence effect. Through the characterization of the three compounds, it is found that the organic solvents such as tetrahydrofuran, toluene and DMF have good solubility, which also provides a good basis for us to further connect the terminal groups. M1OM2OM3 has a high fluorescence quantum efficiency in organic solvents. For example, in tetrahydrofuran solution, the fluorescence quantum efficiency is 0.94 ~ 0.93 ~ 0.91 in turn. In addition, after adding tetrastyrene, M3 compounds showed good agglomeration induced fluorescence in DMF solvent, but M1 and M2 had no agglomeration induced luminescence. It is also shown that the intermolecular interaction and the nonradiative attenuation in the nano-aggregate state can be weakened by the insertion of the group with AIE effect, and the fluorescence is enhanced. On the other hand, the intermolecular planarity of tetrastyrene decreases, and the two-photon absorption cross section M _ 3 excited at 820 nm is slightly smaller than that of M _ 1 and M _ 2. However, when tetrastyrene is introduced, the molecular conjugation system increases and the intramolecular charge transfer increases. The fluorescence emission redshift has a wide range of two-photon absorption in the low band region (880nm), which is superior to M _ 1 and M _ 2. Then, I _ 4H _ 5H _ 5 M _ 6 compounds were synthesized with DPP as the core. We have selected diphenylamine groups which are stronger than trianiline, and finally introduced tetrastyrene groups with AIE effect. The characterization results show that because trianiline has better distortion than diphenylamine, although tetrastyrene group is introduced at last, M6 compounds do not exhibit the good aggregation induced luminescence effect as that of M3 compounds. This is due to diphenylamine group making M 6 molecular flatness superior to M 3 compounds. Compared with compound M _ 4N _ 5, the quenching effect of compound M _ 6 was slowed down by the addition of tetrastyrene, which led to the transition of molecule from ACQ to AIE effect. At 880 nm, the two-photon absorption cross section of compound M6 is as high as 618 GM, while that of M3 compounds is only 237 GM at this wavelength.
【学位授予单位】：青岛科技大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O626
本文编号：2172826
[Abstract]:As a kind of organic dyes, pyrrolidine dione (DPP) has its unique advantages. This is due to the fact that DPP is a high performance dye with bright color, strong light stability, chemical resistance, good thermal stability and easy synthesis. In the past few years, DPP has attracted considerable interest. DPP derivatives have been widely used in the field of (OFETs), two-photon absorption materials, fluorescence probes and so on for (OSCs), field-effect transistors of organic solar cells. In this paper, six compounds M1 to M6 centered on DPP have been designed in order to make a breakthrough and progress in the aggregation induction effect of DPP derivatives and the properties of large two-photon absorption cross sections. Firstly, the target molecule M _ (1) M _ (2) M _ (2) M _ (3) was synthesized by introducing trianiline groups with the ability to give electrons and tetrastyrene groups with strong distorted molecular structure and aggregation induced luminescence effect. Through the characterization of the three compounds, it is found that the organic solvents such as tetrahydrofuran, toluene and DMF have good solubility, which also provides a good basis for us to further connect the terminal groups. M1OM2OM3 has a high fluorescence quantum efficiency in organic solvents. For example, in tetrahydrofuran solution, the fluorescence quantum efficiency is 0.94 ~ 0.93 ~ 0.91 in turn. In addition, after adding tetrastyrene, M3 compounds showed good agglomeration induced fluorescence in DMF solvent, but M1 and M2 had no agglomeration induced luminescence. It is also shown that the intermolecular interaction and the nonradiative attenuation in the nano-aggregate state can be weakened by the insertion of the group with AIE effect, and the fluorescence is enhanced. On the other hand, the intermolecular planarity of tetrastyrene decreases, and the two-photon absorption cross section M _ 3 excited at 820 nm is slightly smaller than that of M _ 1 and M _ 2. However, when tetrastyrene is introduced, the molecular conjugation system increases and the intramolecular charge transfer increases. The fluorescence emission redshift has a wide range of two-photon absorption in the low band region (880nm), which is superior to M _ 1 and M _ 2. Then, I _ 4H _ 5H _ 5 M _ 6 compounds were synthesized with DPP as the core. We have selected diphenylamine groups which are stronger than trianiline, and finally introduced tetrastyrene groups with AIE effect. The characterization results show that because trianiline has better distortion than diphenylamine, although tetrastyrene group is introduced at last, M6 compounds do not exhibit the good aggregation induced luminescence effect as that of M3 compounds. This is due to diphenylamine group making M 6 molecular flatness superior to M 3 compounds. Compared with compound M _ 4N _ 5, the quenching effect of compound M _ 6 was slowed down by the addition of tetrastyrene, which led to the transition of molecule from ACQ to AIE effect. At 880 nm, the two-photon absorption cross section of compound M6 is as high as 618 GM, while that of M3 compounds is only 237 GM at this wavelength.
【学位授予单位】：青岛科技大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O626
【参考文献】
相关硕士学位论文 前1条
1 赵俊芳;有机材料双光子吸收截面测试方法的研究[D];山东师范大学;2006年
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