本文選題：氟硼二吡咯甲川類化合物 + 手性　； 參考：《北京科技大學》2017年博士論文

【摘要】：近年來,有機發(fā)光材料作為一種重要研究工具因其優(yōu)異的表現(xiàn)而被全世界眾多科學家所認可,從而得到了十分快速的發(fā)展。與無機發(fā)光材料相比,有機發(fā)光材料擁有在可見光區(qū)域內(nèi)較高的摩爾消光系數(shù)、易于修飾和種類繁多等優(yōu)勢,被廣泛應用于多個領域,如化學分析、太陽能轉(zhuǎn)化、有機發(fā)光二極管(OLED)等。因此開發(fā)利用具有優(yōu)良性質(zhì)的有機發(fā)光分子已成為當前倍受關注的研究課題。氟硼二吡咯甲川類(Bodipy)化合物迷人的結(jié)構(gòu)賦予了它們很多獨特的性能,并且,Bodipy類化合物是比較容易被修飾的,Bodipy骨架周邊幾乎所有的位置都可以被修飾,使Bodipy類化合物具有不同的性質(zhì),以達到不同的應用目的。但是,Bodipy類化合物在實際應用中也存在著一定的局限性,例如,化合物的吸收一般局限在470-530 nm,并且較小斯托克斯位移(Stokes shift)使化合物在濃溶液中存在明顯的自吸收現(xiàn)象而使其熒光強度減弱,在固態(tài)中存在聚集誘導的熒光淬滅現(xiàn)象(ACQ)等。這些問題大大限制了這類化合物的應用,因此設計和合成能夠改善這些問題的新型Bodipy類化合物,成為了近年來的研究重點。本論文主要針對在Bodipy類化合物在實際應用中存在的不同問題,設計合成了三類新型的Bodipy類化合物,具體內(nèi)容如下:(1)合成了兩個手性苯并氮雜Bodipy化合物,分別是一個1,1-聯(lián)二萘酚取代的苯并氮雜Bodipy和兩個1,1-聯(lián)二萘酚取代的苯并氮雜Bodipy,并對它們的譜學性質(zhì)進行了研究。通過在Bodipy的周邊共軛上苯環(huán),同時在其周邊引入手性聯(lián)二萘取代基團,得到的苯并氮雜Bodipy在近紅外區(qū)域有了光學活性。于是我們合成了第一例在近紅外區(qū)域有光學活性的手性Bodipy。為了對比研究,我們還合成了一個沒有手性取代基Bodipy作為參照化合物(2)合成了一系列功能化的三芳胺取代的Bodipy類化合物Bodipy-TPA-R(R = BI,BH-OH,BH-COOH)以及參照化合物 Bodipy-TPA。這些功能化的Bodipy化合物在溶液中表現(xiàn)出了相類似的光學性質(zhì),但是由于分子堆積模式和分子間作用力的不同,它們在固態(tài)時卻表現(xiàn)出了不同的性質(zhì)。對于化合物Bodipy-TPA和Bodipy-TPA-BH-COOH而言,它們的晶體中Bodipy骨架結(jié)構(gòu)間沒有有效的面對面的π-π堆積作用,并且分子內(nèi)的轉(zhuǎn)動和三芳胺部分與Bodipy骨架部分的電子轉(zhuǎn)移也都得到了有效的抑制,使這兩個化合物都表現(xiàn)出了明顯的聚集誘導的熒光現(xiàn)象(AIE)和晶體誘導的紅色熒光,它們的晶體絕對熒光量子產(chǎn)率(Ω)分別是19.47%和12.30%。然而,對于化合物Bodipy-TPA-BI和Bodipy-TPA-BH-OH而言,在它們的晶體中,雖然三芳胺部分與Bodipy骨架部分的分子內(nèi)轉(zhuǎn)動也同樣得到了有效的抑制,但是由于兩個平行的Bodipy骨架之間存在部分重疊的面對面的π-π堆積作用,它們的晶體絕對熒光量子產(chǎn)率(Ω)是相對較低的,分別是1.37%和3.40%,并且AIE也不明顯。另外,對于化合物Bodipy-TPA-BH-COOH,將Bodipy的三芳胺取代基進行功能化的修飾之后,其薄膜熒光在鹽酸蒸汽中可以迅速淬滅。(3)通過在Bodipy-TPA的2,6號位置引入不同個數(shù)三芳胺取代基得到了化合物Bodipy-2TPA和Bodipy-3TPA。在溶液中,這兩個化合物的電子吸收光譜相比于參照化合物Bodipy-TPA僅發(fā)生了輕微的紅移,但是熒光卻發(fā)生了明顯的紅移現(xiàn)象。由于存在激發(fā)態(tài)的構(gòu)型弛豫,這兩個化合物都擁有較大的斯托克斯位移,分別為約100 nm和約90 nm。同時,由于在Bodipy骨架周圍引入了體積較大的三芳胺取代基團,使得這兩個化合物的晶體中Bodipy骨架結(jié)構(gòu)間沒有有效的面對面的π-π堆積作用,并且分子內(nèi)的轉(zhuǎn)動和三芳胺部分與Bodipy骨架部分的電子轉(zhuǎn)移也都得到了有效的抑制,使這兩個化合物都表現(xiàn)出了明顯的聚集誘導的熒光現(xiàn)象(AIE)和晶體誘導的紅色熒光,它們的晶體絕對熒光量子產(chǎn)率(Ω)分別是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.

【學位授予單位】：北京科技大學
【學位級別】：博士
【學位授予年份】：2017
【分類號】：O626.13;TQ422

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