發(fā)布時(shí)間：2018-09-09 16:43

【摘要】：基于偶氮吡啶類(lèi)衍生物具有良好的光響應(yīng)性和可作為自組裝的復(fù)合體,本文設(shè)計(jì)并合成了系列的含有偶氮吡啶基團(tuán)的衍生物,通過(guò)掃描電鏡,紫外-可見(jiàn),熒光等對(duì)其組裝的行為及性能進(jìn)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(jié)構(gòu)的偶氮吡啶化合物AP1,AP2,AP4,AP5,用核磁氫譜對(duì)其結(jié)構(gòu)進(jìn)行了表征。通過(guò)加入HCl和改變?nèi)軇⿲?duì)其自組裝行為進(jìn)行了研究,發(fā)現(xiàn)在氯仿溶液中,這四類(lèi)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?nèi)軇┮部勺越M裝成竹葉狀,片狀,纖維狀和纖維束狀等。通過(guò)對(duì)偶氮吡啶化合物的固體熒光測(cè)試,發(fā)現(xiàn)熒光減弱。此外,通過(guò)DSC測(cè)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(fù)合成新的化合物APP3,APP5。通過(guò)紅外、DSC和SEM證明了氫鍵的復(fù)合。利用紫外-可見(jiàn)研究了兩個(gè)復(fù)合物的可逆順?lè)串悩?gòu)。通過(guò)DSC和POM研究發(fā)現(xiàn)單體和復(fù)合物都具有良好的液晶性能。經(jīng)過(guò)圓二色譜(CD)的研究發(fā)現(xiàn),這兩種復(fù)合物都可以組裝成螺旋型的結(jié)構(gòu)。(3)合成了三個(gè)三角型的偶氮吡啶化合物M1,M2,M3,并用核磁表征其結(jié)構(gòu)。凝膠測(cè)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(jī)凝膠。流變測(cè)試發(fā)現(xiàn),M2在正丁醇中形成的凝膠儲(chǔ)能模量最高,在正辛醇中的儲(chǔ)能模量最低;通過(guò)對(duì)凝膠進(jìn)行紫外-可見(jiàn)光測(cè)試,該類(lèi)凝膠的模量均受到紫外光的影響。經(jīng)過(guò)圓二色譜(CD)研究發(fā)現(xiàn),M1,M2,M3,都可通過(guò)自組裝成螺旋結(jié)構(gòu),并隨著柔性鏈的變化而發(fā)生轉(zhuǎn)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(xué)位授予單位】：西華師范大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類(lèi)號(hào)】：O626.32

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本文編號(hào)：2232985