本文選題：咔咯 + 光物理性質(zhì)�。� 參考：《華南理工大學(xué)》2016年碩士論文

【摘要】：咔咯化學(xué)被認(rèn)為是卟啉化學(xué)重要的分支。由于咔咯特殊的光化學(xué)與光物理性質(zhì),使其能夠在熒光探針、光動(dòng)力治療、染料敏化太陽(yáng)能等方面有著潛在的應(yīng)用。重原子效應(yīng),作為影響咔咯光物理性質(zhì)的重要因素,卻鮮有探究。為此,本文基于重原子效應(yīng)對(duì)于咔咯配合物光物理性質(zhì)特別是其潛在的光動(dòng)力治療性能進(jìn)行了深入探究。主要工作內(nèi)容如下:1.合成了三種不同氟原子數(shù)的鎵咔咯,即5,15-二苯基,10-五氟苯基咔咯鎵配合物(1-Ga),5,15-二(五氟苯基),10-苯基咔咯鎵配合物(2-Ga),5,10,15-三(五氟苯基)咔咯鎵配合物(3-Ga),以及三種不同碘原子數(shù)的單羥基咔咯,即10-(2-羥基苯基)-5,15-二(五氟苯基)咔咯4,10-(2-羥基-5-碘苯基)-5,15-二(五氟苯基)咔咯5和10-(2-羥基-3,5二碘苯基)-5,15-二(五氟苯基)咔咯6。并利用紫外可見(jiàn)光分度計(jì)、核磁共振光譜儀以及質(zhì)譜儀對(duì)這些樣品進(jìn)行了表征。2.以鹵代苯溶劑作為外重原子源,結(jié)合紫外可見(jiàn)光譜、穩(wěn)態(tài)和時(shí)間分辨熒光光譜以及飛秒瞬態(tài)吸收光譜等技術(shù)探究了鹵代苯溶劑所引起的外重原子效應(yīng)對(duì)于三種鎵咔咯(1-Ga、2-Ga、3-Ga)光物理性質(zhì)的影響。實(shí)驗(yàn)結(jié)果表明鎵咔咯紫外吸收峰位置主要受鹵代苯溶劑的色散力的影響;而外重原子效應(yīng)對(duì)于熒光性質(zhì)的影響與理論上預(yù)期相一致,即其能夠有效降低鎵咔咯的熒光性質(zhì)導(dǎo)致其相關(guān)參數(shù)如熒光量子產(chǎn)率、熒光壽命等數(shù)值的減小;飛秒瞬態(tài)吸收光譜實(shí)驗(yàn)分析結(jié)果表明,在特定波長(zhǎng)光的激發(fā)下,鎵咔咯與鹵代苯溶劑之間可發(fā)生電子轉(zhuǎn)移反應(yīng),溶劑的重原子效應(yīng)可以減緩電荷分離態(tài)復(fù)合物電荷重組速率。3.利用密度泛函理論(DFT)形象表達(dá)出三種單羥基咔咯結(jié)構(gòu)的不同;紫外可見(jiàn)光譜同樣說(shuō)明鹵代苯溶劑的色散力是影響鎵咔咯電子光譜吸收峰位置的主要因素;熒光發(fā)射光譜與熒光衰減曲線說(shuō)明三種咔咯在不同鹵代苯溶劑中的熒光發(fā)光性質(zhì),通過(guò)計(jì)算,發(fā)現(xiàn)雙碘代咔咯6在碘苯中的熒光量子產(chǎn)率Φf最小(0.00755),說(shuō)明雙重重原子效應(yīng)(內(nèi)與外重原子效應(yīng))具有疊加的削弱熒光的作用。4.采用二苯基蒽(DPA)作為單線態(tài)氧的捕獲劑,定性比較三種單羥基咔咯在鹵代苯溶劑中產(chǎn)生單線態(tài)氧的能力,結(jié)果說(shuō)明,在同一種鹵代苯溶劑中,單碘代咔咯5比無(wú)碘咔咯4以及雙碘咔咯6具有更好的單線態(tài)氧生成能力;而對(duì)于同一種咔咯,其在鹵代苯溶劑中的單線態(tài)氧生成能力有如下規(guī)律:苯氟苯碘苯氯苯溴苯。5.利用穩(wěn)態(tài)紅外發(fā)光法測(cè)定了三種羥基咔咯在鹵代苯溶劑中的單線態(tài)氧的穩(wěn)態(tài)發(fā)光(位于1280 nm)左右,通過(guò)發(fā)光強(qiáng)度反映其單線態(tài)氧的生成能力,結(jié)果表明,在同一溶劑中,單碘羥基咔咯5無(wú)碘羥基咔咯4雙碘羥基咔咯6,這與捕獲劑法所得結(jié)果一致;而對(duì)于不同鹵代苯溶劑,則有以下規(guī)律:苯碘苯≈氟苯氯苯溴苯。6.搭建閃光光解裝置,并利用該裝置測(cè)量了三種羥基咔咯在鹵代苯溶劑中的瞬態(tài)吸收光譜,并通過(guò)特征峰的衰減曲線擬合出在有氧以及無(wú)氧條件下的三重態(tài)壽命τ,進(jìn)而計(jì)算出氧氣猝滅速率常數(shù)Kq,結(jié)果顯示在不同鹵代苯溶劑中,對(duì)于咔咯5和6有如下規(guī)律:Kq(碘苯)Kq(氯苯)Kq(氟苯)Kq(溴苯)。在有氧條件下,6在碘苯中呈現(xiàn)出最短的三重態(tài)壽命以及最大的氧氣猝滅速率常數(shù)。
[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.
【學(xué)位授予單位】：華南理工大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2016
【分類(lèi)號(hào)】：O641.4

【相似文獻(xiàn)】

相關(guān)期刊論文 前10條

1 龍文清,李隆弟,童愛(ài)軍;西維因無(wú)保護(hù)流體室溫q泄獾鬧卦有в陀謝薌戀撓跋靃J];分析化學(xué);2002年10期

2 彭景嚇,黃高凌,張勇,朱亞先;重原子存在下β-環(huán)糊精誘導(dǎo)西維因室溫磷光[J];光譜實(shí)驗(yàn)室;2004年04期

3 魏雁聲;劉長(zhǎng)松;張?zhí)K社;;β-環(huán)糊精誘導(dǎo)室溫膦光法測(cè)定痕量7-甲基喹啉的研究——以1-溴環(huán)己烷作重原子微擾劑[J];分析化學(xué);1991年05期

4 龍文清,李隆弟,童愛(ài)軍;磷光壽命法研究無(wú)保護(hù)流體室溫磷光的重原子效應(yīng)和發(fā)光動(dòng)力學(xué)參數(shù)[J];光譜學(xué)與光譜分析;2001年04期

5 梁曉琴,廖顯威;萘的鹵素取代“重原子效應(yīng)”的紅外及熒光光譜的理論研究[J];四川師范大學(xué)學(xué)報(bào)(自然科學(xué)版);2001年03期

6 陳素娥,黃月君,王新,晉衛(wèi)軍;利用選擇性重原子增強(qiáng)的固體表面發(fā)光技術(shù)同時(shí)測(cè)定痕量吡哌酸和氟哌酸[J];山西大學(xué)學(xué)報(bào)(自然科學(xué)版);1999年02期

7 白小紅,魏雁聲,劉長(zhǎng)松;環(huán)氧溴丙烷作重原子微擾劑環(huán)糊精誘導(dǎo)室溫q泄夥ú舛，

本文編號(hào)：2105937