發(fā)布時間：2018-04-01 02:08

  本文選題：圓偏振發(fā)光　切入點：共軛高分子　出處：《南京大學》2017年博士論文

【摘要】：圓偏振發(fā)光(CPL)是指一個手性發(fā)光系統(tǒng)具有的特殊的光學性質(zhì),它不僅可以表征手性分子激發(fā)態(tài)的結(jié)構(gòu)信息,同時它還在化學探針、3D光學顯示、光存儲、液晶激光器等領域具有巨大的應用前景,因此有關圓偏振發(fā)光材料的研究逐漸成為了當前研究的一個熱點。早期關于圓偏振發(fā)光材料的研究主要集中在手性稀土配合物方面,由于有機手性分子、手性高分子圓偏振發(fā)光材料具有高的熒光量子效率、較易的加工性能、有價值的寬帶發(fā)射和更易結(jié)構(gòu)修飾性等優(yōu)勢,近些年來關于它們的研究受到越來越多的關注。本文設計合成了多種基于有機手性分子和手性熒光高分子的圓偏振材料。第二章以手性1,2-環(huán)己二胺作為手性源,合成了兩種不同連接方式的單體,進而通過鈀催化的Sonogashira反應進一步合成了基于BODIPY結(jié)構(gòu)的四種手性熒光高分子,并研究了它們在四氫呋喃溶液中的光學活性。結(jié)果表明具有共軛雙鍵結(jié)構(gòu)的手性高分子可以展現(xiàn)出鏡像對映的圓二色吸收和圓偏振發(fā)光信號,而不具有共軛雙鍵結(jié)構(gòu)的手性高分子的圓二色吸收和圓偏振發(fā)光信號則是靜默的。這表明共軛的雙鍵結(jié)構(gòu)更有利于手性信號的傳遞,從而使高分子表現(xiàn)出相應的光學活性。第三章工作我們通過鈀催化的Sonogashira反應合成基于聯(lián)萘酚結(jié)構(gòu)的手性共軛高分子,并研究了它們在不同溶劑和不同聚集態(tài)下的圓二色吸收和圓偏振發(fā)光性質(zhì)。結(jié)果顯示手性共軛高分子在不同溶劑和不同聚集態(tài)下均顯示出了圓二色吸收和圓偏振發(fā)光活性,這來源于聯(lián)萘酚手性信號的傳遞,同時它們相應的不對稱因子在不同狀態(tài)下基本保持一致,這表明了手性共軛高分子的手性性質(zhì)受微環(huán)境影響很小。第四章我們將手性氨基酸引入到傒二酰亞胺分子中,并研究了它們在三氯甲烷和三氯甲烷-甲醇溶液中相應的光學活性和形貌特征。該手性分子在純的三氯甲烷溶液中并沒有顯示出圓二色吸收和圓偏振發(fā)光活性,而在聚集態(tài)(三氯甲烷-甲醇混合溶液)中顯示出了強的科頓效應和圓偏振發(fā)光信號。進一步研究其形貌可知,該化合物在聚集態(tài)可以通過分子間的π-π相互作用先自組裝成納米棒,然后進一步自組裝成三維的花狀結(jié)構(gòu),其在聚集態(tài)下展示出的光學活性可能與這一自組裝行為有關。第五章我們首先將手性丙氨酸酯引入1,8-萘二酸酐結(jié)構(gòu)中,接著通過鈀催化的Sonogashira反應合成了新型的1,8-萘酰亞胺結(jié)構(gòu)的芘熒光化合物,并研究了它們在四氫呋喃溶液和聚集態(tài)的圓二色吸收和圓偏振發(fā)光性質(zhì)。該手性分子在四氫呋喃溶液中的圓二色吸收和圓偏振發(fā)光信號是靜默的,而其在聚集態(tài)下能夠通過π-π相互作用自組裝成螺旋納米纖維,并展示出了強的鏡面對映的科頓效應和圓偏振發(fā)光信號。
[Abstract]:Circularly polarized luminescence (CPL) refers to the special optical properties of a chiral luminescence system, which can not only characterize the structure information of the excited states of chiral molecules, but also display and store in the chemical probe 3D optical display.Liquid crystal lasers and other fields have great application prospects, so the research of circularly polarized luminescent materials has gradually become a hot spot.Early studies on circularly polarized luminescent materials mainly focused on chiral rare earth complexes. Because of organic chiral molecules, chiral polymer circularly polarized luminescent materials have high fluorescence quantum efficiency and easy processing properties.In recent years, more and more attention has been paid to the advantages of valuable broadband transmission and easier structural modification.In this paper, a variety of circularly polarized materials based on organic chiral molecules and chiral fluorescent polymers have been designed and synthesized.In chapter 2, two kinds of monomers with different joining modes were synthesized by using chiral 1 / 2-cyclohexane diamine as chiral source. Four chiral fluorescent polymers based on BODIPY structure were further synthesized by palladium catalyzed Sonogashira reaction.Their optical activity in tetrahydrofuran solution was studied.The results show that chiral polymers with conjugated double bond structure can exhibit circular dichroism and circularly polarized luminescence signals.The circular dichroism and circularly polarized luminescence signals of chiral polymers without conjugated double bond structure are silent.It is shown that the conjugated double bond structure is more favorable for the transmission of chiral signals, thus making the polymers exhibit the corresponding optical activity.In chapter 3, we synthesized chiral conjugated polymers based on binaphthol structure by palladium catalyzed Sonogashira reaction, and studied their circular dichroism absorption and circularly polarized luminescence properties in different solvents and different aggregates.The results show that the chiral conjugated polymers exhibit circular dichroism and circularly polarized luminescence activity in different solvents and different aggregation states, which originates from the transmission of binaphthol chiral signals.At the same time, their corresponding asymmetric factors are basically consistent in different states, which indicates that the chiral properties of chiral conjugated polymers are very little affected by microenvironment.In chapter 4, we introduce chiral amino acids into the molecules of maleimide and study their optical activity and morphology in chloroform and trichloromethane-methanol solution.The chiral molecule did not exhibit circular dichroism and circularly polarized luminescence activity in pure trichloromethane solution, but showed strong Coton effect and circularly polarized luminescence signal in the aggregated state (trichloromethane methanol mixed solution).Further study of its morphology shows that the compound can self-assemble into nanorods by 蟺-蟺 interaction between molecules, and then self-assemble into three-dimensional flower-like structures.Its optical activity in the aggregate state may be related to this self-assembly behavior.In chapter 5, we first introduce the chiral alanine ester into the structure of 1'8 naphthalene dichloride, and then we synthesize a new pyrene fluorescent compound with 1'8 'naphthalimide structure by palladium catalyzed Sonogashira reaction.The circular dichroism and circularly polarized luminescence of tetrahydrofuran solution and aggregation state were studied.The circular dichroism absorption and circularly polarized luminescence signals of the chiral molecule in tetrahydrofuran solution are silent, and the chiral molecules can self-assemble into helical nanofibers by 蟺-蟺 interaction in the aggregated state.A strong mirror reflected by the Coton effect and a circularly polarized luminescence signal are also shown.
【學位授予單位】：南京大學
【學位級別】：博士
【學位授予年份】：2017
【分類號】：TQ422

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