金属卟啉轴向配位二噻吩乙烯化合物的合成及光致变色性能研究
发布时间：2018-12-13 03:33
【摘要】：在众多的有机光致变色材料中,二噻吩乙烯类分子因具有良好的热稳定性和抗疲劳性,被广泛认为是最有可能开发成新一代光子存储介质的光致变色材料。有机光致变色材料在实际应用中存在光量子产率低,抗疲劳性差,记录信息在读取后遭到破坏等瓶颈问题,因此,需要在二噻吩乙烯分子中引入其它基团来解决上述问题。文章的主要研究内容如下:(1)以2-甲基噻吩为起始原料经过NCS取代,Friedel-Crafts酰基化,McMurry环化,Suzuki偶联得到目标产物。在整个合成路线中,通过改变最后一步Suzuki偶联反应中的卤代芳烃,即可得到文中合成的三种不对称二噻吩乙烯:1-(2-甲基-5-氯-3-噻吩基)-2-(2-甲基-5-吡啶基-3-噻吩基)环戊烯(PyDTE);1-(2-甲基-5-氯-3-噻吩基)-2-[2-甲基5-(4-氨基苯基)-3-噻吩基]环戊烯(ApDTE);1-(2-甲基-5-氯-3-噻吩基)-2-[2-甲基-5-(4-溴苯基)-3-噻吩基]环戊烯(BpDTE)。(2)研究了(1)中三种二噻吩乙烯的光致变色性能,研究结果表明三种化合物均表现出良好的光致变色性能:能在一定波长照射下进行开、闭环转换,具有很好的重现性;室温条件下具有较好的热稳定性及抗疲劳性。(3)以氯化血红素和四苯基卟啉为原料,分别对它们的结构进行修饰改性,得到锌(Ⅱ)-间卟啉二甲酯[Zn(Ⅱ)MPDME],钴(Ⅱ)-间卟啉二甲酯[Co(Ⅱ)MPDME],,锰(Ⅱ)-四苯基卟啉[Mn(Ⅱ)TPP],该步骤是将卟啉环引入到二噻吩乙烯的关键。(4)利用配位键成功的将金属卟啉轴向配位到吡啶基二噻吩乙烯分子上,得到Zn(Ⅱ)MPDME-PyDTE,Co(Ⅱ)MPDME-PyDTE,Mn(Ⅱ)TPP-PyDTE。研究这三种最终产物的光致变色性能,并探究了它们在无损读取方面的性能。与(2)中的吡啶基二噻吩乙烯的紫外-可见吸收光谱对比,发现所得三种配合物的紫外-可见谱图均发生明显的红移,开、闭环异构体的最大吸收波长间距变大。由于信息无损读取的前提是写、读、擦三个过程所在光区间相互独立、互不干扰。分析发现,只有Mn(Ⅱ)TPP-PyDTE满足上述条件,有望应用于信息的无损读取中。
[Abstract]:Among many organic photochromic materials, dithiophene ethylene molecules are widely considered to be the most likely photochromic materials to be developed into a new generation of photonic storage media because of their good thermal stability and fatigue resistance. In the practical application of organic photochromic materials, there are some bottleneck problems, such as low quantum yield, poor fatigue resistance and destruction of recording information. Therefore, other groups should be introduced into dithiophene to solve the above problems. The main contents of this paper are as follows: (1) the target product was obtained by NCS substitution, Friedel-Crafts acylation, McMurry cyclization and Suzuki coupling using 2-methylthiophene as the starting material. By changing the halogenated aromatics in the last step of the Suzuki coupling reaction, Three asymmetric dithiophene ethylene, 1- (2-methyl-5-chloro-3-thiophenyl) -2- (2-methyl-5-pyridyl-3-thiophenyl) cyclopentene (PyDTE);, were synthesized in this paper. 1- (2-methyl-5-chloro-3-thiophenyl) -2- [2-methyl-5- (4-aminophenyl) -3-thiophenyl] cyclopentene (ApDTE); 1- (2-methyl-5-chloro-3-thiophene) -2- [2-methyl-5- (4-bromophenyl) -3-thiophenyl] cyclopentene (BpDTE). (_ 2) the photochromic properties of three dithiophene ethylene in (1) were studied. The results show that the three compounds exhibit good photochromic properties: they can be switched on and off under certain wavelength irradiation and have good reproducibility; It has good thermal stability and fatigue resistance at room temperature. (3) Zn (鈪，
本文编号：2375796
[Abstract]:Among many organic photochromic materials, dithiophene ethylene molecules are widely considered to be the most likely photochromic materials to be developed into a new generation of photonic storage media because of their good thermal stability and fatigue resistance. In the practical application of organic photochromic materials, there are some bottleneck problems, such as low quantum yield, poor fatigue resistance and destruction of recording information. Therefore, other groups should be introduced into dithiophene to solve the above problems. The main contents of this paper are as follows: (1) the target product was obtained by NCS substitution, Friedel-Crafts acylation, McMurry cyclization and Suzuki coupling using 2-methylthiophene as the starting material. By changing the halogenated aromatics in the last step of the Suzuki coupling reaction, Three asymmetric dithiophene ethylene, 1- (2-methyl-5-chloro-3-thiophenyl) -2- (2-methyl-5-pyridyl-3-thiophenyl) cyclopentene (PyDTE);, were synthesized in this paper. 1- (2-methyl-5-chloro-3-thiophenyl) -2- [2-methyl-5- (4-aminophenyl) -3-thiophenyl] cyclopentene (ApDTE); 1- (2-methyl-5-chloro-3-thiophene) -2- [2-methyl-5- (4-bromophenyl) -3-thiophenyl] cyclopentene (BpDTE). (_ 2) the photochromic properties of three dithiophene ethylene in (1) were studied. The results show that the three compounds exhibit good photochromic properties: they can be switched on and off under certain wavelength irradiation and have good reproducibility; It has good thermal stability and fatigue resistance at room temperature. (3) Zn (鈪，
本文编号：2375796
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