發(fā)布時(shí)間：2019-03-05 12:27

【摘要】：偶氮苯化合物是一種典型的光致變色材料,其光致異構(gòu)化特性在諸多領(lǐng)域得到了廣泛的應(yīng)用。本文設(shè)計(jì)合成了五種不同結(jié)構(gòu)的偶氮苯衍生物,著重探討了其結(jié)構(gòu)對(duì)光譜性能的影響。在此基礎(chǔ)上,將偶氮苯的光致異構(gòu)化性能應(yīng)用于無機(jī)量子點(diǎn)以及石墨烯的改性。首先,我們采用了重氮偶合法合成了五種不同的偶氮苯衍生物,其中包括含有強(qiáng)吸電子基團(tuán)、給電子基團(tuán)以及含有不同數(shù)目偶氮基的化合物。合成過程中也涉及到氨基的氧化、氨基保護(hù)以及硝基還原。目標(biāo)產(chǎn)物通過紅外和紫外-可見吸收光譜進(jìn)行了分析表征。其次,偶氮苯化合物的光致異構(gòu)化性能主要與分子結(jié)構(gòu)上取代基的性質(zhì)有關(guān)。我們分別對(duì)含有吸電子基團(tuán)-NO2、給電子基團(tuán)-NH2以及不同數(shù)目偶氮基的化合物的光致異構(gòu)化動(dòng)力學(xué)行為進(jìn)行了比較研究,發(fā)現(xiàn)不同性質(zhì)的取代基對(duì)化合物光致異構(gòu)化性能的影響不同,吸電子基團(tuán)具有抑制作用,而多個(gè)偶氮基團(tuán)的作用較為復(fù)雜。此外,溶劑的極性以及酸性對(duì)偶氮苯化合物的紫外-吸收光譜存在一定的影響。極性溶劑的極化作用影響了分子中電子躍遷的能量差,導(dǎo)致譜帶的最大吸收波長(λmax)發(fā)生位移；介質(zhì)中的H+使分子中的生色團(tuán)質(zhì)子化,化學(xué)鍵發(fā)生改變,從而產(chǎn)生酸致變色現(xiàn)象。然后,在對(duì)無機(jī)量子點(diǎn)的改性方面,我們將具有良好光致異構(gòu)化性能的4-氨基偶氮苯與巰基丙酸(MPA)通過酰胺化縮合反應(yīng)制成新的偶氮苯化合物(MPAA),并通過1HNMR、FTIR以及UV-Vis光譜對(duì)其結(jié)構(gòu)進(jìn)行表征分析。將這種化合物與MPA共同作為配體制備了CdSe-MPAA量子點(diǎn)。與單純以MPA作為配體合成的CdSe量子相比,在紫外-可見吸收光譜中,新型量子點(diǎn)具有光致異構(gòu)化特性；在熒光光譜中,偶氮苯分子的加入對(duì)CdSe量子點(diǎn)的熒光起到了猝滅效應(yīng)。最后,在對(duì)氧化石墨烯(GO)功能化方面,我們利用了GO表面上大量的極性親水基團(tuán)-COOH和4,4’-二氨基偶氮苯通過酰胺化縮合反應(yīng),將偶氮苯分子接枝到GO表面,制成GO-Azo雜化材料。這種材料同時(shí)具有GO的單片層基本結(jié)構(gòu)和偶氮苯生色團(tuán)的光致異構(gòu)化行為。功能化的GO-Azo的電導(dǎo)率與GO相比顯著提高,并在紫外光作用下的電導(dǎo)率逐漸下降,說明可將其應(yīng)用于光控電導(dǎo)率研究。
[Abstract]:Azobenzene compounds are a typical photochromic material, and their photoisomerization properties have been widely used in many fields. In this paper, five azobenzene derivatives with different structures have been designed and synthesized, and the effect of their structures on the spectral properties has been discussed emphatically. On this basis, the photoisomerization of azobenzene was applied to the modification of inorganic quantum dots and graphene. Firstly, we synthesized five different azobenzene derivatives by diazo coupling method, including strong electron-absorbing group, donor group and compound containing different number of azobenzene groups. The synthesis process also involves the oxidation of amino group, protection of amino group and reduction of nitro group. The target products were characterized by IR and UV-vis absorption spectra. Secondly, the photoisomerization properties of azobenzene compounds are mainly related to the properties of substituents in molecular structure. The photoisomerization kinetics of compounds containing electron-absorbing group-NO2, donor group-NH2 and different number of azo groups were compared. It is found that different substituents have different effects on the properties of photoisomerization of compounds, and the electron-absorbing groups have inhibitory effect, while the effects of several azo groups are more complex. In addition, the polarity of the solvent and the UV-absorption spectra of azobenzene compounds were affected to a certain extent. The polarization of polar solvent affects the energy difference of electron transition in molecule, which results in the shift of maximum absorption wavelength (位 max). The H in the medium makes the chromophore in the molecule protonated and the chemical bond changes, resulting in an acid-induced discoloration phenomenon. Then, in the modification of inorganic quantum dots, 4-aminoazobenzene with mercaptopropionic acid (MPA), which has good photoisomerization properties, was synthesized by amidation condensation reaction to form a new azobenzene compound (MPAA), and passed 1HNMR. The structure was characterized by FTIR and UV-Vis spectra. The CdSe-MPAA quantum dots were prepared by co-using this compound with MPA as ligand. Compared with CdSe quantum synthesized only with MPA as ligand, the novel quantum dots have the properties of photoisomerization in UV-vis absorption spectra, and the fluorescence of CdSe QDs is quenched by the addition of azobenzene molecules in the fluorescence spectra. Finally, in the aspect of (GO) functionalization of graphene oxide, we used a large number of polar hydrophilic groups-COOH and 4,4-diaminylazobenzene on the surface of GO to graft azobenzene onto GO surface by amidation condensation reaction. GO-Azo hybrid material was made. This material has both the basic lamellar structure of GO and the photoisomerization of azobenzene chromophore. The conductivity of functionalized GO-Azo is significantly higher than that of GO, and the conductivity decreases gradually under the action of ultraviolet light, which indicates that it can be applied to the study of photo-controlled conductivity.
【學(xué)位授予單位】：中國海洋大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類號(hào)】：O625.65

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