本文選題：咔唑 + 雜原子[5]螺烯　； 參考：《山東大學(xué)》2017年碩士論文

【摘要】：螺烯是一類獨(dú)特的具有手性的稠環(huán)芳香化合物。螺烯分子的手性結(jié)構(gòu)、非平面π-電子體系的離域效應(yīng)來源于螺旋排布的芳環(huán)骨架結(jié)構(gòu)。螺烯化合物具有良好的旋光性、圓二色性、非線性光學(xué)性能以及自組裝成超分子材料的能力,展現(xiàn)出非凡的光電性能和氧化還原性能;在非線性光學(xué)材料、液晶材料、手性光學(xué)材料以及有機(jī)電致發(fā)光材料等方面展現(xiàn)出良好的應(yīng)用前景。雜原子[n]螺烯是一個(gè)或多個(gè)苯環(huán)被相應(yīng)雜環(huán)取代而形成的一類螺烯。這類螺烯由于在固態(tài)時(shí)表現(xiàn)出自組裝行為,即可與過渡金屬離子形成配合物而引起人們的研究興趣。這意味著雜原子[5]螺烯能作為一種發(fā)光材料應(yīng)用于有機(jī)光電子器件和傳感器。本論文研究的主要內(nèi)容是兩種新穎的雜原子[5]螺烯類化合物:8-己基-噻吩并[3',2':3,4]苯并[1,2-c]咔唑和9-己基-4,9-二氮雜-茚并[2,1-c]菲的設(shè)計(jì)、合成、表征與性能研究。2,12-二噻吩-5,15-二己基-5,15-二氮雜[7]螺烯化合物的量化計(jì)算結(jié)果的分析也包含其中�；衔�8-己基-噻吩并[3',2'3,4]苯并[1,2-c]咔唑是目前已報(bào)道的第一種基于咔唑的硫-氮雜[5]螺烯類化合物。我們以3-溴咔唑和2-乙烯基噻吩為起始反應(yīng)原料,通過3-溴咔唑N烷基化、Heck反應(yīng)和光催化閉環(huán)反應(yīng)三步反應(yīng),合成了 8-己基-噻吩并[3',2'3,4]苯并[l,2-c]咔唑類化合物。我們完成了化合物的表征(1H NMR、13C NMR、HRMS),并對(duì)化合物的光學(xué)性能(紫外-可見吸收和熒光發(fā)射光譜)、電化學(xué)性能和熱學(xué)性能進(jìn)行測(cè)試與研究�；衔镌谡和�、甲苯、二氯甲烷、乙酸乙酯、乙腈、甲醇中的最大吸收峰在298～301 nm范圍內(nèi);最大發(fā)射峰在402～406 nm范圍內(nèi);在薄膜狀態(tài)下,最大發(fā)射峰位于407 nm處,都處于紫光范圍內(nèi)。在二氯甲烷中,化合物獲得了最大的熒光量子產(chǎn)率,可達(dá)33.7%。在電化學(xué)測(cè)試中,化合物經(jīng)歷了不可逆的氧化還原過程,其HOMO能級(jí)為-4.81 eV,LUMO能級(jí)為-1.67 eV。熱學(xué)性質(zhì)測(cè)試結(jié)果表明化合物的Td為:236.16℃�；衔�9-己基-4,9-二氮雜-茚并[2,l-c]菲是首次合成的基于咔唑的二氮雜[5]螺烯類化合物。我們以3-溴咔唑和2-乙烯基吡啶為起始反應(yīng)原料,通過3-溴咔唑N烷基化、Heck反應(yīng)和光催化閉環(huán)反應(yīng)三步反應(yīng),合成了 9-己基-4,9-二氮雜-茚并[2,1-c]菲類化合物。我們完成了化合物的1HNMR、13CNMR、HRMS的測(cè)試,并對(duì)化合物的光學(xué)性能(紫外-可見吸收和熒光發(fā)射光譜)、電化學(xué)性能和熱學(xué)性能進(jìn)行測(cè)試和研究�；衔镌谡和�、甲苯、二氯甲烷、乙酸乙酯、乙腈中的最大吸收峰在306～321 nm范圍內(nèi);最大發(fā)射峰在400～427 nm范圍內(nèi);熒光量子產(chǎn)率處于9.0%～M3.3%范圍。然而薄膜狀態(tài)的最大發(fā)射峰位于518 nm處。在電化學(xué)測(cè)試中,化合物經(jīng)歷了不可逆的氧化還原過程,其HOMO能級(jí)為-5.28 eV,LUMO能級(jí)為-2.26eV。熱分析曲線表明化合物的Td為:206.31℃。我們對(duì)2,12-二噻吩-5,15-二己基-5,15-二氮雜[7]螺烯化合物進(jìn)行了量化計(jì)算。我們得到了化合物在二氯甲烷中的紫外-可見吸收光譜、分子的前線軌道以及電子能級(jí)、振子強(qiáng)度等結(jié)果。理論計(jì)算結(jié)果與我們的實(shí)驗(yàn)測(cè)試數(shù)據(jù)吻合得較好。通過分析我們可以得出:最強(qiáng)吸收峰和次強(qiáng)吸收峰主要來源于HOMO-2-LUMO(4.0449 eV)、HOMO-1→LUMO(3.9051 eV)和 HOMO→LUMO+1(3.8296 eV)電子躍遷。
[Abstract]:Spirene is a unique class of chiral polycyclic aromatic compounds. The chiral structure of the spirene molecule. The off domain effect of the non planar pi electron system derives from the aromatic ring skeleton structure of the spiral arrangement. The spirenes exhibit good optical activity, circular two color, nonlinear optical properties and the ability to self assemble into supermolecular materials. Remarkable optoelectronic properties and redox properties; good applications have been shown in nonlinear optical materials, liquid crystal materials, chiral optical materials, and organic electroluminescent materials. The heteroatom [n] spirene is a class of spirenes formed by the substitution of corresponding heterocyclic rings for one or more benzene rings. This type of spirene is derived from the solid state. The assembly behavior can cause research interest in the formation of complexes with transition metal ions. This means that the heteroatom [5] spirene can be used as a kind of luminescent material in organic optoelectronic devices and sensors. The main content of this paper is two novel heteroatom [5] spirenes: 8- hexyl thiophene, [3', 2': 3,4] benzene The design, synthesis, characterization and properties of [1,2-c] carbazole and 9- hexyl -4,9- two azo and [2,1-c] phenanthrene, analysis of the quantitative calculation results of.2,12- two thiophene -5,15- two hexyl -5,15- two n-hetero [7] stud compound, including compounds 8- hexyl thiophene, [3', 2'3,4] benzo [1,2-c] carbazole is the first reported based on the present report [5] bromo carbazole and 2- vinyl thiophene are used as starting materials for carbazole. We synthesized 8- hexyl thiophene and [3', 2'3,4] benzo and [l, and 2-c] carbazole by N alkylation of bromo carbazole with 3-, N alkylation of 3- bromo carbazole, Heck reaction and photocatalytic closed loop reaction. MS) and test and study the optical properties of the compounds (UV visible absorption and fluorescence emission), electrochemical properties and thermal properties. The maximum absorption peak in n-hexane, toluene, dichloromethane, ethyl acetate, acetonitrile and methanol is within the range of 298~301 nm; the maximum emission peak is within the range of 402~406 nm, and the film state is in the film state. The maximum emission peak is located at 407 nm and in the range of violet light. In dichloromethane, the compound obtained the maximum fluorescence quantum yield, which can reach 33.7%. in the electrochemical test, the compound has undergone irreversible redox process, its HOMO energy level is -4.81 eV, and LUMO energy level is -1.67 eV. thermal properties test results of the compound Td At 236.16, the compound 9- hexyl -4,9- two nanzine and [2, l-c] phenanthrene is the first synthesis of two aza [5] spirenes based on carbazole. We use 3- bromo carbazole and 2- vinyl pyridine as starting reaction materials, 3- bromo carbazole N alkylation, Heck reaction and photocatalytic closed loop reaction three step reaction, synthesis of 9- hexyl -4,9- two aza - Nene. And [2,1-c] phenanthrene compounds. We completed the tests of the compounds' 1HNMR, 13CNMR, HRMS, and tested and studied the optical properties of the compounds (UV visible absorption and fluorescence emission), electrochemical properties and thermal properties. The maximum absorption peaks in n-hexane, toluene, two chloromethane, ethyl acetate and acetonitrile were 306~321 Within the range of nm, the maximum emission peak is within the range of 400~427 nm; the fluorescence quantum yield is in the range of 9% to M3.3%. However, the maximum emission peak of the film state is located at 518 nm. In the electrochemical test, the compound has undergone an irreversible redox process, and its HOMO level is -5.28 eV, and LUMO energy level is -2.26eV. thermal analysis curve indicating T of the compound's T. D is: at 206.31 C, we have quantified the 2,12- two thiophene -5,15- two hexyl -5,15- two nitrogen heterozygous compounds. We obtained the UV visible absorption spectra of the compounds in dichloromethane, the front-line orbit of the molecules, the electronic energy level, the oscillator strength and so on. The theoretical calculation coincides with our experimental data. It is good that we can conclude that the strongest absorption peak and secondary strong absorption peak are mainly derived from HOMO-2-LUMO (4.0449 eV), HOMO-1 to LUMO (3.9051 eV) and HOMO to LUMO+1 (3.8296 eV) electron transition.
【學(xué)位授予單位】：山東大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O626

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本文編號(hào)：1906402