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  本文選題：光致變色化合物　切入點：二噻吩乙烯　出處：《南京理工大學(xué)》2017年碩士論文　論文類型：學(xué)位論文

【摘要】：在一定波長光的照射下,有機(jī)光致變色化合物能夠在兩種異構(gòu)體之間進(jìn)行可逆的轉(zhuǎn)化,可用于信息存儲器件中,實現(xiàn)光調(diào)控下的信息超高速存儲。二噻吩乙烯類光致變色化合物具有優(yōu)異熱穩(wěn)定性和耐疲勞性,被認(rèn)為是最有可能實用化的有機(jī)光信息儲存材料。信息無損讀取的實現(xiàn)是二噻吩乙烯類光致變色化合物用作信息儲存材料時所面臨的首要問題。信息讀取的方法眾多,熒光調(diào)控讀取信息的方法因具有響應(yīng)速度快和靈敏度高的優(yōu)點而被科學(xué)家們廣泛采用。由于二噻吩乙烯本身不具備發(fā)射熒光的能力,因此需要引入發(fā)色團(tuán),卟啉類化合物具有良好的光、熱穩(wěn)定性和光電性能,在其特征S帶或Q帶光激發(fā)下能發(fā)射出強(qiáng)烈熒光,是一類理想的熒光發(fā)色團(tuán)。基于此,本文設(shè)計將四苯基卟啉通過共價鍵引入二噻吩乙烯分子中,改善其無損讀取性能,具體研究內(nèi)容如下:(1)5-氯-2-甲基噻吩與戊二酰氯經(jīng)過傅克反應(yīng)和McMurry反應(yīng)合成了 1,2-雙(5-氯-2-甲基-3-噻吩基)環(huán)戊烯,探討了每步反應(yīng)的影響因素并予以優(yōu)化。(2)發(fā)煙硝酸硝化四苯基卟啉,并用SnCl2還原硝化產(chǎn)物,得5-(4-氨基苯基)-10,15,20-三苯基卟啉,探討了硝化過程的影響因素,并予以優(yōu)化。二酰亞胺還原氨基卟啉,合成5-(4-氨基苯基)-10,15,20-三苯二氫卟啉。(3)1,2-雙(5-氯-2-甲基-3-噻吩基)環(huán)戊烯和5-(4-氨基苯基)-10,15,20-三苯基卟啉先后經(jīng)過縮合和Suzuki反應(yīng)合成了 1-(2-甲基-3-噻吩基)-2-[2-甲基-5-[4-[4-(10,15,20-三苯基-5-卟啉基)苯基]氨基羰基苯基]-3-噻吩基]環(huán)戊烯,目標(biāo)產(chǎn)物結(jié)構(gòu)經(jīng)1HNMR、13CNMR、MS和IR表征確認(rèn),通過紫外-可見光譜研究了化合物的光致變色性能、抗疲勞性和熱穩(wěn)定性,并輔以熒光光譜探究了化合物的無損讀取功能。實驗結(jié)果表明,該化合物在254和660 nm的光照射下,發(fā)生可逆的光致變色反應(yīng),重復(fù)光照8次后其紫外-可見光譜與初始譜圖相比無明顯差異,顯示出良好的抗疲勞性;當(dāng)激發(fā)光為520nm時,開、閉環(huán)異構(gòu)體有較高的熒光對比度,有望實現(xiàn)數(shù)據(jù)的無損讀取。
[Abstract]:Under the irradiation of certain wavelength light, organic photochromic compounds can be reversible converted between the two isomers and can be used in information storage devices. The photochromic dithiophene compounds have excellent thermal stability and fatigue resistance. It is considered to be the most practical organic light information storage material. The realization of information lossless reading is the first problem when dithiophene vinyl photochromic compounds are used as information storage materials. There are many methods for information reading. The method of reading information by fluorescence regulation is widely used by scientists because of its fast response speed and high sensitivity. Because dithiophene itself does not have the ability to emit fluorescence, it is necessary to introduce chromophore. Porphyrins have good photoluminescence, thermal stability and optoelectronic properties. They can emit strong fluorescence under the excitation of their characteristic S-band or Q-band light, so they are a kind of ideal fluorescent chromophore. In this paper, tetraphenylporphyrins were introduced into dithiophene via covalent bonds to improve their nondestructive reading properties. The main contents of the study are as follows: the synthesis of 1 ~ (2 +) -dichloro-5-chloro-2-methyl-3-thiophenyl) cyclopentene was synthesized by Fourier reaction and McMurry reaction with glutaryl chloride. The influencing factors of each step reaction were discussed and optimized. 2) nitration of tetraphenylporphyrin with fuming nitric acid was carried out, and the product of nitration was reduced by SnCl2. Diimide reduced aminoporphyrin, Synthesis of 1-2-methyl-3-thiophenyl-2-dihydroporphyrin [2-methyl-5- [4- [4- 101010101015- triphenylporphyrin] -2-methyl-5-chloro-5-chloro-2-methyl-3-thiophenyl) cyclopentene by condensation and Suzuki reaction was synthesized by the condensation and Suzuki reaction of 5-O4-4-Aminophenyl-1015- (1-2-methyl-3-thiophenyl) -2- [2-methyl-5- [4- [4-101015- 20- triphenyl -5-]) -1-2-methyl-3-thiophenyl (2-methyl-5-) -1-2-methyl-3-thiophenyl (2-methyl-5- [4- [4- [4-101015- 20- triphenyl -5-]). Porphyrinyl) phenyl] amino carbonyl phenyl] -3-thiophene > cyclopentene, The structure of the target product was characterized by 1HNMR-13CNMR-MS and IR. The photochromic properties, fatigue resistance and thermal stability of the compounds were studied by UV-Vis spectroscopy, and the nondestructive reading function of the compounds was investigated by fluorescence spectroscopy. Under the irradiation of 254 nm and 660 nm, the compound showed reversible photochromic reaction. After repeated illumination for 8 times, the UV-Vis spectrum showed no significant difference compared with the initial spectrum, and showed good fatigue resistance, and when the excitation light was 520 nm, the photochromic reaction was turned on. Closed-loop isomers have high fluorescence contrast, which is expected to achieve lossless reading of data.
【學(xué)位授予單位】：南京理工大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O626

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