本文關(guān)鍵詞：含噻吩基席夫堿類化合物的合成及其光化學(xué)性能研究　出處：《新疆大學(xué)》2015年碩士論文　論文類型：學(xué)位論文

  更多相關(guān)文章： 光致變色 噻吩 苯基氨基脲 氨基硫脲衍生物 熒光

【摘要】：有機(jī)光致變色材料是一類在光信息存儲(chǔ)、分子開(kāi)關(guān)、光學(xué)鏡片、光學(xué)防偽等領(lǐng)域最具有應(yīng)用潛力的高性能功能材料。目前大量研究集中在對(duì)已有的光致變色化合物進(jìn)行改性和復(fù)合,然而新的化合物的合成、新的光致變色體系的開(kāi)發(fā)仍然是推動(dòng)這一領(lǐng)域發(fā)展的動(dòng)力。本文以噻吩基席夫堿化合物為研究對(duì)象,合成了11種新化合物,并對(duì)這些化合物的組成、結(jié)構(gòu)與光化學(xué)性能進(jìn)行了表征和測(cè)試,分析了化合物的光致變色機(jī)理,總結(jié)了這類化合物的結(jié)構(gòu)與光化學(xué)性能之間的關(guān)系,為新型光致變色材料的研究、開(kāi)發(fā)與應(yīng)用提供了科學(xué)依據(jù)和理論基礎(chǔ)。第一章合成了9個(gè)噻吩甲醛縮氨基硫脲類化合物。利用1H-NMR、13C-NMR、質(zhì)譜、X-ray單晶衍射表征了這些化合物的組成與結(jié)構(gòu),采用紫外-可見(jiàn)吸收光譜和熒光發(fā)射光譜分析了這些化合物的光化學(xué)性能及反應(yīng)動(dòng)力學(xué)。發(fā)現(xiàn)3個(gè)噻吩甲醛縮氨基硫脲化合物在固態(tài)下具有紫外光變色,可見(jiàn)光消色的光致變色性能,討論了噻吩環(huán)5位的取代基對(duì)化合物光致變色速率的影響,并運(yùn)用變色前后的紅外譜圖和單晶結(jié)構(gòu),解釋了其變色機(jī)理;其它6個(gè)噻吩甲醛縮甲基氨基硫脲和噻吩甲醛縮苯基氨基硫脲化合物在固態(tài)下均不具有光致變色性能,但具有有機(jī)小分子發(fā)光性能,并運(yùn)用理論計(jì)算解釋了化合物的發(fā)光機(jī)理;選擇了一種熒光性能最好的化合物噻吩-2-甲醛縮苯基氨基硫脲S2C-PTSC與聚苯乙烯(PS)復(fù)合,制備了一種具有與粉末相同性能的薄膜。此外,我們還發(fā)現(xiàn)了噻吩-2-甲醛縮苯基氨基硫脲3個(gè)化合物在溶液中具有光致變色性能,探討了溶劑極性對(duì)其變色性能的影響。第二章在前一部分的基礎(chǔ)上,在噻吩上引入了一個(gè)苯環(huán),合成了2種光致變色化合物:苯并噻吩-2-甲醛縮4-苯基氨基脲[BS2C-PSC]和苯并噻吩-2-甲酮縮4-苯基氨基脲[BS2T-PSC]光致變色化合物。通過(guò)對(duì)它們的組成、結(jié)構(gòu)及性能進(jìn)行研究,發(fā)現(xiàn)化合物BS2T-PSC具有不可逆的變色性能,而化合物BS2C-PSC具有紫外光變色和可見(jiàn)光褪色的光致變色性能,同時(shí)還具有熱增幅現(xiàn)象、熒光性能和良好的抗疲勞性能。根據(jù)晶體結(jié)構(gòu)和變色前后的紅外光譜,提出了該類化合物的變色機(jī)理為酮式與醇式結(jié)構(gòu)互變的質(zhì)子轉(zhuǎn)移。此外,將化合物BS2C-PSC與聚苯乙烯復(fù)合制備出了一種與粉末具有相似性質(zhì)的薄膜,在信息存儲(chǔ)和智能窗簾等領(lǐng)域具有潛在的應(yīng)用。
[Abstract]:Organic photochromic materials are a class of optical information storage, molecular switches, optical lenses. Optical anti-counterfeiting and other fields have the most potential of high-performance functional materials. At present, a large number of studies focused on the existing photochromic compounds to modify and composite, however, the synthesis of new compounds. The development of new photochromic system is still the driving force to promote the development of this field. In this paper, 11 new compounds have been synthesized and their compositions have been studied by taking thiophene Schiff base compounds as the research object. The structure and photochemical properties were characterized and tested, the photochromic mechanism of the compounds was analyzed, and the relationship between the structure and photochemical properties of these compounds was summarized, which is a new type of photochromic materials. In chapter 1, nine thiophene formaldehyde thiosemicarbazones were synthesized. 1H-NMR-13C-NMR-MS was used. The composition and structure of these compounds were characterized by X-ray single crystal diffraction. The photochemical properties and reaction kinetics of these compounds were analyzed by UV-Vis absorption spectra and fluorescence emission spectra. It was found that three thiophene formaldehyde thiosemicarbazone compounds had UV photochromism in solid state. The photochromic properties of visible photochromic compounds are discussed. The influence of the 5-position substituents of thiophene ring on the photochromic rate of the compounds is discussed. The mechanism of photochromic reaction is explained by the infrared spectra and single crystal structure before and after discoloration. The other six thiophene formaldehyde methyl thiosemicarbazone and thiophene formaldehyde phenyl thiosemicarbazone compounds have no photochromic properties in the solid state, but have the photoluminescence properties of organic small molecules. The luminescence mechanism of the compounds was explained by theoretical calculation. A novel compound, thiophene -2-formaldehyde thiosemicarbazone (S2C-PTSC) and polystyrene (PS), was selected to prepare a thin film with the same properties as the powder. We also found that thiophene-2-formaldehyde phenylthiosemicarbazone had photochromic properties in solution and discussed the effect of solvent polarity on its discoloration performance. Chapter 2 was based on the former part. Two photochromic compounds, benzothiophene -2-formaldehyde, 4-phenylsemicarbazone, were synthesized by introducing a benzene ring into thiophene. [BS2C-PSC] and benzothiophene 2-methyl ketone 4-phenylsemicarbazone. [By studying the composition, structure and properties of photochromic compounds, it is found that compound BS2T-PSC has irreversible discoloration property. The compound BS2C-PSC has the photochromic properties of UV and visible light fading, and also has the phenomenon of thermal increase. According to the crystal structure and infrared spectrum before and after discoloration, the chromotropic mechanism of this kind of compounds is the proton transfer between ketone and alcohol. A kind of thin film with similar properties to powder was prepared by compound BS2C-PSC and polystyrene, which has potential applications in the field of information storage and intelligent curtain.
【學(xué)位授予單位】：新疆大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類號(hào)】：O626.12;TB34

【參考文獻(xiàn)】

相關(guān)期刊論文 前1條

1 孟康;錢鷹;;雙枝[1,3,4]-VA二唑衍生物的合成與熒光性質(zhì)[J];有機(jī)化學(xué);2009年01期

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本文編號(hào)：1392076