基于咔唑的螺烯化合物的合成、表征及性质研究

发布时间：2018-05-18 15:34

本文选题：咔唑 + 杂原子[5]螺烯　；参考：《山东大学》2017年硕士论文

【摘要】：螺烯是一类独特的具有手性的稠环芳香化合物。螺烯分子的手性结构、非平面π-电子体系的离域效应来源于螺旋排布的芳环骨架结构。螺烯化合物具有良好的旋光性、圆二色性、非线性光学性能以及自组装成超分子材料的能力,展现出非凡的光电性能和氧化还原性能;在非线性光学材料、液晶材料、手性光学材料以及有机电致发光材料等方面展现出良好的应用前景。杂原子[n]螺烯是一个或多个苯环被相应杂环取代而形成的一类螺烯。这类螺烯由于在固态时表现出自组装行为,即可与过渡金属离子形成配合物而引起人们的研究兴趣。这意味着杂原子[5]螺烯能作为一种发光材料应用于有机光电子器件和传感器。本论文研究的主要内容是两种新颖的杂原子[5]螺烯类化合物:8-己基-噻吩并[3',2':3,4]苯并[1,2-c]咔唑和9-己基-4,9-二氮杂-茚并[2,1-c]菲的设计、合成、表征与性能研究。2,12-二噻吩-5,15-二己基-5,15-二氮杂[7]螺烯化合物的量化计算结果的分析也包含其中。化合物8-己基-噻吩并[3',2'3,4]苯并[1,2-c]咔唑是目前已报道的第一种基于咔唑的硫-氮杂[5]螺烯类化合物。我们以3-溴咔唑和2-乙烯基噻吩为起始反应原料,通过3-溴咔唑N烷基化、Heck反应和光催化闭环反应三步反应,合成了 8-己基-噻吩并[3',2'3,4]苯并[l,2-c]咔唑类化合物。我们完成了化合物的表征(1H NMR、13C NMR、HRMS),并对化合物的光学性能(紫外-可见吸收和荧光发射光谱)、电化学性能和热学性能进行测试与研究。化合物在正己烷、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范围内;最大发射峰在402～406 nm范围内;在薄膜状态下,最大发射峰位于407 nm处,都处于紫光范围内。在二氯甲烷中,化合物获得了最大的荧光量子产率,可达33.7%。在电化学测试中,化合物经历了不可逆的氧化还原过程,其HOMO能级为-4.81 eV,LUMO能级为-1.67 eV。热学性质测试结果表明化合物的Td为:236.16℃。化合物9-己基-4,9-二氮杂-茚并[2,l-c]菲是首次合成的基于咔唑的二氮杂[5]螺烯类化合物。我们以3-溴咔唑和2-乙烯基吡啶为起始反应原料,通过3-溴咔唑N烷基化、Heck反应和光催化闭环反应三步反应,合成了 9-己基-4,9-二氮杂-茚并[2,1-c]菲类化合物。我们完成了化合物的1HNMR、13CNMR、HRMS的测试,并对化合物的光学性能(紫外-可见吸收和荧光发射光谱)、电化学性能和热学性能进行测试和研究。化合物在正己烷、甲苯、二氯甲烷、乙酸乙酯、乙腈中的最大吸收峰在306～321 nm范围内;最大发射峰在400～427 nm范围内;荧光量子产率处于9.0%～M3.3%范围。然而薄膜状态的最大发射峰位于518 nm处。在电化学测试中,化合物经历了不可逆的氧化还原过程,其HOMO能级为-5.28 eV,LUMO能级为-2.26eV。热分析曲线表明化合物的Td为:206.31℃。我们对2,12-二噻吩-5,15-二己基-5,15-二氮杂[7]螺烯化合物进行了量化计算。我们得到了化合物在二氯甲烷中的紫外-可见吸收光谱、分子的前线轨道以及电子能级、振子强度等结果。理论计算结果与我们的实验测试数据吻合得较好。通过分析我们可以得出:最强吸收峰和次强吸收峰主要来源于HOMO-2-LUMO(4.0449 eV)、HOMO-1→LUMO(3.9051 eV)和 HOMO→LUMO+1(3.8296 eV)电子跃迁。
[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.
【学位授予单位】：山东大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O626

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