重原子效应对于咔咯及其镓配合物光物理性质的影响

发布时间：2018-07-07 18:57

本文选题：咔咯 + 光物理性质　；参考：《华南理工大学》2016年硕士论文

【摘要】：咔咯化学被认为是卟啉化学重要的分支。由于咔咯特殊的光化学与光物理性质,使其能够在荧光探针、光动力治疗、染料敏化太阳能等方面有着潜在的应用。重原子效应,作为影响咔咯光物理性质的重要因素,却鲜有探究。为此,本文基于重原子效应对于咔咯配合物光物理性质特别是其潜在的光动力治疗性能进行了深入探究。主要工作内容如下:1.合成了三种不同氟原子数的镓咔咯,即5,15-二苯基,10-五氟苯基咔咯镓配合物(1-Ga),5,15-二(五氟苯基),10-苯基咔咯镓配合物(2-Ga),5,10,15-三(五氟苯基)咔咯镓配合物(3-Ga),以及三种不同碘原子数的单羟基咔咯,即10-(2-羟基苯基)-5,15-二(五氟苯基)咔咯4,10-(2-羟基-5-碘苯基)-5,15-二(五氟苯基)咔咯5和10-(2-羟基-3,5二碘苯基)-5,15-二(五氟苯基)咔咯6。并利用紫外可见光分度计、核磁共振光谱仪以及质谱仪对这些样品进行了表征。2.以卤代苯溶剂作为外重原子源,结合紫外可见光谱、稳态和时间分辨荧光光谱以及飞秒瞬态吸收光谱等技术探究了卤代苯溶剂所引起的外重原子效应对于三种镓咔咯(1-Ga、2-Ga、3-Ga)光物理性质的影响。实验结果表明镓咔咯紫外吸收峰位置主要受卤代苯溶剂的色散力的影响;而外重原子效应对于荧光性质的影响与理论上预期相一致,即其能够有效降低镓咔咯的荧光性质导致其相关参数如荧光量子产率、荧光寿命等数值的减小;飞秒瞬态吸收光谱实验分析结果表明,在特定波长光的激发下,镓咔咯与卤代苯溶剂之间可发生电子转移反应,溶剂的重原子效应可以减缓电荷分离态复合物电荷重组速率。3.利用密度泛函理论(DFT)形象表达出三种单羟基咔咯结构的不同;紫外可见光谱同样说明卤代苯溶剂的色散力是影响镓咔咯电子光谱吸收峰位置的主要因素;荧光发射光谱与荧光衰减曲线说明三种咔咯在不同卤代苯溶剂中的荧光发光性质,通过计算,发现双碘代咔咯6在碘苯中的荧光量子产率Φf最小(0.00755),说明双重重原子效应(内与外重原子效应)具有叠加的削弱荧光的作用。4.采用二苯基蒽(DPA)作为单线态氧的捕获剂,定性比较三种单羟基咔咯在卤代苯溶剂中产生单线态氧的能力,结果说明,在同一种卤代苯溶剂中,单碘代咔咯5比无碘咔咯4以及双碘咔咯6具有更好的单线态氧生成能力;而对于同一种咔咯,其在卤代苯溶剂中的单线态氧生成能力有如下规律:苯氟苯碘苯氯苯溴苯。5.利用稳态红外发光法测定了三种羟基咔咯在卤代苯溶剂中的单线态氧的稳态发光(位于1280 nm)左右,通过发光强度反映其单线态氧的生成能力,结果表明,在同一溶剂中,单碘羟基咔咯5无碘羟基咔咯4双碘羟基咔咯6,这与捕获剂法所得结果一致;而对于不同卤代苯溶剂,则有以下规律:苯碘苯≈氟苯氯苯溴苯。6.搭建闪光光解装置,并利用该装置测量了三种羟基咔咯在卤代苯溶剂中的瞬态吸收光谱,并通过特征峰的衰减曲线拟合出在有氧以及无氧条件下的三重态寿命τ,进而计算出氧气猝灭速率常数Kq,结果显示在不同卤代苯溶剂中,对于咔咯5和6有如下规律:Kq(碘苯)Kq(氯苯)Kq(氟苯)Kq(溴苯)。在有氧条件下,6在碘苯中呈现出最短的三重态寿命以及最大的氧气猝灭速率常数。
[Abstract]:Carbazole chemistry is considered to be an important branch of porphyrin chemistry. Because of the special photochemical and photophysical properties of carbazole, it has potential applications in fluorescent probes, photodynamic therapy, and dye-sensitized solar energy. The heavy atom effect is rarely explored as an important factor affecting the physical properties of carbazole light. This paper is based on this paper. The heavy atomic effect has been deeply explored for the photophysical properties of the carbazole complexes, especially their potential photodynamic therapy. The main contents are as follows: 1. the synthesis of three gallium carbazole with different fluorine atoms, namely, 5,15- two phenyl, 10- five fluoro phenyl carbazine complex (1-Ga), 5,15- two (five fluoro phenyl), 10- phenyl carbazine complex (2-) Ga), 5,10,15- three (five fluoro phenyl) carbazine complex (3-Ga), and three kinds of single hydroxyl carbazole with different iodine atoms, that is, 10- (2- hydroxy phenyl) -5,15- two (five fluoro phenyl) carbazole 4,10- (2- hydroxyl -5- iodiphenyl) -5,15- two (five fluorin phenyl) carbazole 5 and 10- (2- hydroxyl two iodiphenyl) two (five fluorphenyl) two (five fluorphenyl) carbazole 6. and ultraviolet visible light Spectrometers, NMR spectroscopy and mass spectrometers were used to characterize these samples by using halogenated benzene as external heavy atomic sources, UV visible spectra, steady-state and time resolved fluorescence spectra and femtosecond transient absorption spectroscopy to explore the effect of the external heavy atom effect on three kinds of gallium (1-Ga, 2-). The effects of Ga, 3-Ga) on the photophysical properties. The experimental results show that the location of gallium carbazole UV absorption peak is mainly influenced by the dispersion force of the halogenated benzene solvent, but the effect of the external heavy atom effect on the fluorescence properties is consistent with the theoretical expectation, that is, it can effectively reduce the fluorescence properties of gallium carbazole and lead to the related parameters, such as fluorescence quantum yield, fluorescence. The results of the femtosecond transient absorption spectra show that the electron transfer reaction can occur between gallium carbazol and halogenated benzene under the excitation of a specific wavelength of light, and the heavy atom effect of the solvent can slow the charge recombination rate of the charge separation complex.3. by using the density functional theory (DFT) image to express three The UV visible spectrum also shows that the dispersion force of the halogenated benzene solvent is the main factor affecting the absorption peak position of the gallium carbazol electron spectrum, and the fluorescence emission spectrum and the fluorescence attenuation curve illustrate the fluorescence properties of three kinds of Carbazole in different halogenated benzene solvents. By calculation, it is found that the double iodic carbazole is 6 in iodine. The fluorescence quantum yield of benzene is minimum (0.00755) (0.00755), indicating that the double heavy atom effect (internal and external heavy atom effect) has the superimposed weakening of fluorescence,.4. uses two phenyl anthracene (DPA) as a single wire oxygen capture agent, and compares the ability of three single hydroxyl carbazoles to produce singlet oxygen in the halogenated solvent. The results show that the same species is in the same kind. In the halogenated benzene solvent, the single iodine carbazole 5 ratio no iodine carbazole 4 and the double iodine carbazole 6 have the better single wire oxygen generation ability; and for the same kind of carbazole, the single wire oxygen generation ability in the halogenated benzene solvent has the following regularity: the benzodiphenyl chlorobenzobenzobenzene.5. uses the steady red external luminescence method to determine three hydroxyl carbazol in halogenated benzene. The steady state luminescence of the single state oxygen in the solvent (located at 1280 nm) reflects the generating ability of the single wire oxygen by the luminescence intensity. The results show that in the same solvent, the single iodine hydroxyl carbazol 5 No iodine hydroxyl carbazole 4 double iodine hydroxyl chlorin 6, which is the result of the result obtained by the capture agent method; and for the different halogenated benzene solvent, there is the following law: benzene iodine The flash photolysis device was set up by benzo fluorobenzobenzobbrobenzene.6., and the device was used to measure the transient absorption spectra of three kinds of hydroxyl carbazol in the halogenated benzene solvent, and the three state lifetime tau under the oxygen and oxygen free conditions was fitted by the attenuation curve of the characteristic peak, and the oxygen quenching rate constant Kq was calculated. The results showed that the different halogen was in different halogen. In the benzol solvent, there are the following rules for carbazole 5 and 6: Kq (iodine) Kq (chlorobenzene) Kq (fluorobenzene) Kq (bromo benzene). Under aerobic conditions, 6 in iodine benzene presents the shortest three heavy state life and the maximum oxygen quenching rate constant.
【学位授予单位】：华南理工大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O641.4

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