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基于偶氮吡啶類衍生物的合成及自組裝行為的研究

發(fā)布時間:2018-09-09 16:43
【摘要】:基于偶氮吡啶類衍生物具有良好的光響應性和可作為自組裝的復合體,本文設計并合成了系列的含有偶氮吡啶基團的衍生物,通過掃描電鏡,紫外-可見,熒光等對其組裝的行為及性能進行了表征。現(xiàn)將工作概括如下:(1)合成了系列含柔性鏈烴基和膽固醇結構的偶氮吡啶化合物AP1,AP2,AP4,AP5,用核磁氫譜對其結構進行了表征。通過加入HCl和改變溶劑對其自組裝行為進行了研究,發(fā)現(xiàn)在氯仿溶液中,這四類化合物與鹽酸自組裝后的形貌分別為纖維狀,條狀,短棒狀和纖維束等;改變溶劑也可自組裝成竹葉狀,片狀,纖維狀和纖維束狀等。通過對偶氮吡啶化合物的固體熒光測試,發(fā)現(xiàn)熒光減弱。此外,通過DSC測試,發(fā)現(xiàn)加酸前后AP1,AP2,AP5都具有良好的液晶性。(2)由于吡啶環(huán)上的氮原子能夠與羥基形成氫鍵,將合成的偶氮吡啶化合物AP3,AP5分別與間苯三酚以氫鍵的形式復合成新的化合物APP3,APP5。通過紅外、DSC和SEM證明了氫鍵的復合。利用紫外-可見研究了兩個復合物的可逆順反異構。通過DSC和POM研究發(fā)現(xiàn)單體和復合物都具有良好的液晶性能。經過圓二色譜(CD)的研究發(fā)現(xiàn),這兩種復合物都可以組裝成螺旋型的結構。(3)合成了三個三角型的偶氮吡啶化合物M1,M2,M3,并用核磁表征其結構。凝膠測試發(fā)現(xiàn)M1,M2,M3分別在正丁醇,正戊醇和正辛醇都可以形成有機凝膠。流變測試發(fā)現(xiàn),M2在正丁醇中形成的凝膠儲能模量最高,在正辛醇中的儲能模量最低;通過對凝膠進行紫外-可見光測試,該類凝膠的模量均受到紫外光的影響。經過圓二色譜(CD)研究發(fā)現(xiàn),M1,M2,M3,都可通過自組裝成螺旋結構,并隨著柔性鏈的變化而發(fā)生轉變。
[Abstract]:Based on the excellent photoresponse of azopyridine derivatives and their self-assembly properties, a series of derivatives containing azopyridine groups were designed and synthesized. The assembly behavior and properties were characterized by fluorescence. The work is summarized as follows: (1) A series of azopyridine compounds with flexible chain hydrocarbon and cholesterol structures have been synthesized and characterized by nuclear magnetic hydrogen spectroscopy (NMR). The self-assembly behavior was studied by adding HCl and changing solvent. It was found that in chloroform solution, the self-assembled morphology of these four compounds and hydrochloric acid were fibrous, strip, short rod and fiber bundles respectively. The modified solvent can also be self-assembled into bamboo leaf, flake, fibrous and fibrous bundles. The fluorescence of azopyridine compounds was detected by solid state fluorescence test. In addition, DSC results show that AP1,AP2,AP5 has good liquid crystal properties before and after adding acid. (2) because nitrogen atoms in pyridine ring can form hydrogen bonds with hydroxyl groups, Synthesis of azopyridine compound AP3,AP5 and isoglucinol in the form of hydrogen bonding to form a new compound APP3,APP5. The composite of hydrogen bond was proved by IR DSC and SEM. The reversible cis-trans isomerization of two complexes was studied by UV-vis. The results of DSC and POM show that both the monomer and the composite have good liquid crystal properties. It was found by circular dichroism (CD) that both of the complexes could be assembled into helical structures. (3) three triangulated azopyridine compounds M _ (1) M _ (2) O _ (2) M _ (3) were synthesized and their structures were characterized by NMR. It was found that the organic gels were formed in n-butanol, n-pentanol and n-octanol, respectively. Rheological tests show that M _ 2 has the highest storage modulus in n-butanol and the lowest in n-octanol. By circular dichroism (CD), it was found that M1OM2M3 can be self-assembled into helical structure and change with the change of flexible chain.
【學位授予單位】:西華師范大學
【學位級別】:碩士
【學位授予年份】:2017
【分類號】:O626.32

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