【摘要】：在眾多的有機(jī)光致變色材料中,二噻吩乙烯類分子因具有良好的熱穩(wěn)定性和抗疲勞性,被廣泛認(rèn)為是最有可能開發(fā)成新一代光子存儲介質(zhì)的光致變色材料。有機(jī)光致變色材料在實際應(yīng)用中存在光量子產(chǎn)率低,抗疲勞性差,記錄信息在讀取后遭到破壞等瓶頸問題,因此,需要在二噻吩乙烯分子中引入其它基團(tuán)來解決上述問題。文章的主要研究內(nèi)容如下:(1)以2-甲基噻吩為起始原料經(jīng)過NCS取代,Friedel-Crafts�；�,McMurry環(huán)化,Suzuki偶聯(lián)得到目標(biāo)產(chǎn)物。在整個合成路線中,通過改變最后一步Suzuki偶聯(lián)反應(yīng)中的鹵代芳烴,即可得到文中合成的三種不對稱二噻吩乙烯:1-(2-甲基-5-氯-3-噻吩基)-2-(2-甲基-5-吡啶基-3-噻吩基)環(huán)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]環(huán)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]環(huán)戊烯(BpDTE)。(2)研究了(1)中三種二噻吩乙烯的光致變色性能,研究結(jié)果表明三種化合物均表現(xiàn)出良好的光致變色性能:能在一定波長照射下進(jìn)行開、閉環(huán)轉(zhuǎn)換,具有很好的重現(xiàn)性;室溫條件下具有較好的熱穩(wěn)定性及抗疲勞性。(3)以氯化血紅素和四苯基卟啉為原料,分別對它們的結(jié)構(gòu)進(jìn)行修飾改性,得到鋅(Ⅱ)-間卟啉二甲酯[Zn(Ⅱ)MPDME],鈷(Ⅱ)-間卟啉二甲酯[Co(Ⅱ)MPDME],,錳(Ⅱ)-四苯基卟啉[Mn(Ⅱ)TPP],該步驟是將卟啉環(huán)引入到二噻吩乙烯的關(guān)鍵。(4)利用配位鍵成功的將金屬卟啉軸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。研究這三種最終產(chǎn)物的光致變色性能,并探究了它們在無損讀取方面的性能。與(2)中的吡啶基二噻吩乙烯的紫外-可見吸收光譜對比,發(fā)現(xiàn)所得三種配合物的紫外-可見譜圖均發(fā)生明顯的紅移,開、閉環(huán)異構(gòu)體的最大吸收波長間距變大。由于信息無損讀取的前提是寫、讀、擦三個過程所在光區(qū)間相互獨(dú)立、互不干擾。分析發(fā)現(xiàn),只有Mn(Ⅱ)TPP-PyDTE滿足上述條件,有望應(yīng)用于信息的無損讀取中。
[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，

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