本文選題：聚炔 + 手性��； 參考：《深圳大學(xué)》2017年碩士論文

【摘要】：本論文通過(guò)合理的分子設(shè)計(jì)將熒光基團(tuán)和手性中心通過(guò)側(cè)鏈修飾的方式引入到聚炔分子中,成功合成了兩類(lèi)具有聚集誘導(dǎo)發(fā)光(Aggregation-Induced Emission,簡(jiǎn)稱(chēng)AIE)特性的炔類(lèi)聚合物,在對(duì)其分子結(jié)構(gòu)表征的基礎(chǔ)上探討了手性及發(fā)光行為,主要內(nèi)容分章節(jié)介紹如下:第一章主要介紹了聚炔化合物的結(jié)構(gòu)、合成及催化劑類(lèi)型,當(dāng)在聚炔化合物結(jié)構(gòu)中引入手性基團(tuán),會(huì)賦予圓二色性、圓偏振發(fā)光等分子特殊光學(xué)活性和物理性質(zhì)。另外還簡(jiǎn)述了傳統(tǒng)熒光材料的結(jié)構(gòu)特征:具有大共軛、平面結(jié)構(gòu)等特點(diǎn),導(dǎo)致傳統(tǒng)的熒光材料在集聚態(tài)或固態(tài)下熒光猝滅,從而限制了其實(shí)際的應(yīng)用;為了解決這個(gè)問(wèn)題,引出新型的AIE熒光材料。第二章簡(jiǎn)述了本論文實(shí)驗(yàn)過(guò)程中所使用的試劑、儀器和表征方法。第三章合成四個(gè)四苯基乙烯的手性側(cè)鏈烷基炔單體,并通過(guò)自制的金屬配位催化劑Rh+(nbd)[B(C6H6)4]-得到分子量大(Mw)、分子量分布適中的四個(gè)側(cè)鏈修飾的聚乙炔高分子。首先,對(duì)聚合物進(jìn)行了光譜表征,實(shí)驗(yàn)表明:在溶液含水量小于20%時(shí),熒光很弱;之后,其熒光強(qiáng)度隨含水量的增加而劇增。另一方面,在CD(Circular Dichroism)光譜上可以明顯看到Cotton效應(yīng),說(shuō)明手性中心的不對(duì)稱(chēng)性已經(jīng)傳遞到主鏈上去。接著,通過(guò)向聚合物溶液中加入劣溶劑的方法觀測(cè)了其CD信號(hào)的變化趨勢(shì),發(fā)現(xiàn)這些聚合物的CD響應(yīng)都隨劣溶劑含量的增加而減弱,在薄膜狀態(tài)下CD信號(hào)甚至完全消失。另外,通過(guò)混合溶劑制樣方法,能夠在電鏡下找到由聚合物分子自組裝形成的螺旋結(jié)構(gòu)。作者還對(duì)單體的光譜行為和手性性質(zhì)進(jìn)行了表征,結(jié)果表明:單體具有明顯的AIE特征和手性。第四章對(duì)四個(gè)四苯基乙烯的手性側(cè)鏈苯乙炔聚合物進(jìn)行研究,使用自制的金屬配位催化劑[Rh(cod)2Cl]2完成聚合。但因結(jié)構(gòu)特點(diǎn)的約束最終只得到一個(gè)分子量大(Mw),分子量分布適中的側(cè)鏈修飾聚苯乙炔分子。首先,對(duì)聚合物的研究發(fā)現(xiàn):其熒光強(qiáng)度隨劣溶劑含量的增加而增強(qiáng),在CD光譜上表現(xiàn)出曲線(xiàn)的正負(fù)交替,具有AICD(Aggregation-induced Circular Dichroism)的性質(zhì),但薄膜的CD響應(yīng)則完全消失。其次,其形貌研究發(fā)現(xiàn),聚合物能自組裝成有孔的微米球。最后,作者對(duì)單體的熒光及手性特征進(jìn)行了表征,研究表明:單體具有顯著的AIE活性和手性。第五章對(duì)論文實(shí)驗(yàn)和結(jié)果進(jìn)行了系統(tǒng)總結(jié)和探討。
[Abstract]:In this paper, fluorescence groups and chiral centers were introduced into polyacetylene molecules by side chain modification through reasonable molecular design, and two kinds of acetylene polymers with agglomeration-induced Aggregation-Induced Emissionation (AIEs) were successfully synthesized. On the basis of characterization of molecular structure, chiral and luminescent behaviors are discussed. The main contents are as follows: in Chapter 1, the structure, synthesis and catalyst types of polyacetylene compounds are introduced. When chiral groups are introduced into the structure of polyacetylene compounds, circular dichroism, circularly polarized luminescence and other special optical and physical properties will be given. In addition, the structural characteristics of traditional fluorescent materials are briefly described, such as large conjugation, planar structure and so on, which lead to fluorescence quenching of traditional fluorescent materials in concentrated or solid state, which limits their practical application. A new type of AIE fluorescent material was obtained. In the second chapter, the reagents, instruments and characterization methods used in the experiment are briefly described. In chapter 3, four chiral side chain alkyne monomers of tetraphenylethylene were synthesized, and four modified polyacetylene polymers with high molecular weight and moderate molecular weight distribution were obtained by using the self-made metal coordination catalyst Rh nbd) [B(C6H6)4]. The results show that the fluorescence is weak when the water content of the solution is less than 20, and then the fluorescence intensity increases sharply with the increase of the water content. On the other hand, the Cotton effect can be seen in the CD(Circular Dichrois spectra, indicating that the asymmetry of the chiral center has been transferred to the main chain. Then, by adding inferior solvent into polymer solution, the change trend of CD signal was observed. It was found that the CD response of these polymers decreased with the increase of the content of inferior solvent, and the CD signal disappeared completely in the film state. In addition, the helical structure formed by self-assembly of polymer molecules can be found under electron microscope by mixed solvent preparation method. The spectral behavior and chiral properties of the monomers were also characterized. The results showed that the monomers had obvious AIE characteristics and chiral properties. In chapter 4, the chiral side chain phenylacetylene polymers of four tetraphenyl ethylene were studied. The polymerization was completed by using the metal coordination catalyst [Rh(cod)2Cl] 2 made by ourselves. However, due to the restriction of structural characteristics, only a large molecular weight MwN with a moderate molecular weight distribution can be obtained by side chain modification of polyphenylene acetylene. Firstly, it is found that the fluorescence intensity of the polymer increases with the increase of the content of the inferior solvent, and the CD spectra show the positive or negative alternation of the curves, which have the properties of AICD(Aggregation-induced Circular Dichrois m), but the CD response of the films disappears completely. Secondly, it is found that the polymer can self-assemble into microspheres with pores. Finally, the fluorescence and chiral properties of the monomers were characterized. The results showed that the monomers had significant AIE activity and chirality. In the fifth chapter, the experiment and results are summarized and discussed systematically.
【學(xué)位授予單位】：深圳大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類(lèi)號(hào)】：O632.17

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