基于吡咯并吡咯二酮的衍生物設計合成及其光學性質(zhì)的研究
發(fā)布時間：2018-08-08 19:32
【摘要】：吡咯并吡咯二酮(DPP)作為有機染料的一種,有著其獨特的優(yōu)勢。這是由于DPP是一種有著色澤鮮艷、光穩(wěn)定性強、耐化學藥品、熱穩(wěn)定好、易于合成的高性能的染料。在過去的幾年里DPP引起了相當大的研究興趣。DPP衍生物廣泛的被應用在有機太陽能電池(OSCs),場效應晶體管(OFETs),雙光子吸收材料,熒光探針等領域。本文設計了六個以DPP為中心的化合物M1到M6,目的是在DPP衍生物在聚集誘導效應和大的雙光子吸收截面性能上有一定的突破和進展。首先合成了目標分子M1,M2,M3,通過引入有給電子能力的三苯胺基團和具有強扭曲分子結構的和聚集誘導發(fā)光效應的四苯乙烯基團。通過對三種化合物的表征得出,在有機溶劑如四氫呋喃,甲苯,DMF等有良好的溶解性,這也為我們進一步接入端基提供了好的基礎。M1,M2,M3在有機溶劑中有很高的熒光量子效率,如在四氫呋喃溶液中熒光量子效率依次為0.94,0.93,0.91。另外,接入四苯乙烯后M3化合物在水含量不斷加入到DMF溶劑中表現(xiàn)出了良好的聚集誘導熒光的特點,而M1與M2沒有聚集誘導發(fā)光的特點,這也表明了通過接入具有AIE效應的基團能夠使分子的平面性減弱,分子間相互作用減弱,在納米聚集態(tài),非輻射衰減減弱,使熒光增強。而四苯乙烯的接入分子平面性減弱,在820 nm波長激發(fā)雙光子吸收截面化合物M3稍小于M1與M2,但是由于在四苯乙烯引入后,分子共軛體系增大,分子內(nèi)電荷轉(zhuǎn)移增強,熒光發(fā)射紅移,在低波段區(qū)域(880nm),有很寬的雙光子吸收范圍,優(yōu)于化合物M1和M2。然后又以DPP為核心合成了M4,M5,M6化合物。我們選用了比三苯胺的給電子能力更強的二苯胺基團,最后引入具有AIE效應的四苯乙烯基團。通過表征我們得出由于三苯胺的扭曲性比二苯胺好,所以雖然最后引入了四苯乙烯基團,但是M6化合物沒有表現(xiàn)出像M3化合物那樣的良好的聚集誘導發(fā)光效應。這源于二苯胺基團使M6分子平面性優(yōu)于M3化合物。同化合物M4,M5比較,四苯乙烯的接入使化合物M6淬滅效應減緩,有使分子從ACQ向AIE效應轉(zhuǎn)變的趨勢。在雙光吸收特點上,M6分子在880 nm波長激發(fā),化合物M6的雙光子吸收截面高達618 GM,而M3化合物在這個波長上激發(fā)僅有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.
【學位授予單位】：青島科技大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O626
本文編號：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.
【學位授予單位】：青島科技大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O626
【參考文獻】
相關碩士學位論文 前1條
1 趙俊芳;有機材料雙光子吸收截面測試方法的研究[D];山東師范大學;2006年
，本文編號：2172826
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