基于四苯基卟啉改性的二噻吩乙烯化合物的设计、合成与性质研究

发布时间：2018-03-04 23:21

本文选题：光致变色化合物　切入点：二噻吩乙烯　出处：《南京理工大学》2017年硕士论文　论文类型：学位论文

【摘要】：在一定波长光的照射下,有机光致变色化合物能够在两种异构体之间进行可逆的转化,可用于信息存储器件中,实现光调控下的信息超高速存储。二噻吩乙烯类光致变色化合物具有优异热稳定性和耐疲劳性,被认为是最有可能实用化的有机光信息储存材料。信息无损读取的实现是二噻吩乙烯类光致变色化合物用作信息储存材料时所面临的首要问题。信息读取的方法众多,荧光调控读取信息的方法因具有响应速度快和灵敏度高的优点而被科学家们广泛采用。由于二噻吩乙烯本身不具备发射荧光的能力,因此需要引入发色团,卟啉类化合物具有良好的光、热稳定性和光电性能,在其特征S带或Q带光激发下能发射出强烈荧光,是一类理想的荧光发色团。基于此,本文设计将四苯基卟啉通过共价键引入二噻吩乙烯分子中,改善其无损读取性能,具体研究内容如下:(1)5-氯-2-甲基噻吩与戊二酰氯经过傅克反应和McMurry反应合成了 1,2-双(5-氯-2-甲基-3-噻吩基)环戊烯,探讨了每步反应的影响因素并予以优化。(2)发烟硝酸硝化四苯基卟啉,并用SnCl2还原硝化产物,得5-(4-氨基苯基)-10,15,20-三苯基卟啉,探讨了硝化过程的影响因素,并予以优化。二酰亚胺还原氨基卟啉,合成5-(4-氨基苯基)-10,15,20-三苯二氢卟啉。(3)1,2-双(5-氯-2-甲基-3-噻吩基)环戊烯和5-(4-氨基苯基)-10,15,20-三苯基卟啉先后经过缩合和Suzuki反应合成了 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]环戊烯,目标产物结构经1HNMR、13CNMR、MS和IR表征确认,通过紫外-可见光谱研究了化合物的光致变色性能、抗疲劳性和热稳定性,并辅以荧光光谱探究了化合物的无损读取功能。实验结果表明,该化合物在254和660 nm的光照射下,发生可逆的光致变色反应,重复光照8次后其紫外-可见光谱与初始谱图相比无明显差异,显示出良好的抗疲劳性;当激发光为520nm时,开、闭环异构体有较高的荧光对比度,有望实现数据的无损读取。
[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.
【学位授予单位】：南京理工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O626

【参考文献】