基于有机手性分子圆偏振发光材料的设计、合成与性质研究

发布时间：2018-04-01 02:08

本文选题：圆偏振发光　切入点：共轭高分子　出处：《南京大学》2017年博士论文

【摘要】：圆偏振发光(CPL)是指一个手性发光系统具有的特殊的光学性质,它不仅可以表征手性分子激发态的结构信息,同时它还在化学探针、3D光学显示、光存储、液晶激光器等领域具有巨大的应用前景,因此有关圆偏振发光材料的研究逐渐成为了当前研究的一个热点。早期关于圆偏振发光材料的研究主要集中在手性稀土配合物方面,由于有机手性分子、手性高分子圆偏振发光材料具有高的荧光量子效率、较易的加工性能、有价值的宽带发射和更易结构修饰性等优势,近些年来关于它们的研究受到越来越多的关注。本文设计合成了多种基于有机手性分子和手性荧光高分子的圆偏振材料。第二章以手性1,2-环己二胺作为手性源,合成了两种不同连接方式的单体,进而通过钯催化的Sonogashira反应进一步合成了基于BODIPY结构的四种手性荧光高分子,并研究了它们在四氢呋喃溶液中的光学活性。结果表明具有共轭双键结构的手性高分子可以展现出镜像对映的圆二色吸收和圆偏振发光信号,而不具有共轭双键结构的手性高分子的圆二色吸收和圆偏振发光信号则是静默的。这表明共轭的双键结构更有利于手性信号的传递,从而使高分子表现出相应的光学活性。第三章工作我们通过钯催化的Sonogashira反应合成基于联萘酚结构的手性共轭高分子,并研究了它们在不同溶剂和不同聚集态下的圆二色吸收和圆偏振发光性质。结果显示手性共轭高分子在不同溶剂和不同聚集态下均显示出了圆二色吸收和圆偏振发光活性,这来源于联萘酚手性信号的传递,同时它们相应的不对称因子在不同状态下基本保持一致,这表明了手性共轭高分子的手性性质受微环境影响很小。第四章我们将手性氨基酸引入到傒二酰亚胺分子中,并研究了它们在三氯甲烷和三氯甲烷-甲醇溶液中相应的光学活性和形貌特征。该手性分子在纯的三氯甲烷溶液中并没有显示出圆二色吸收和圆偏振发光活性,而在聚集态(三氯甲烷-甲醇混合溶液)中显示出了强的科顿效应和圆偏振发光信号。进一步研究其形貌可知,该化合物在聚集态可以通过分子间的π-π相互作用先自组装成纳米棒,然后进一步自组装成三维的花状结构,其在聚集态下展示出的光学活性可能与这一自组装行为有关。第五章我们首先将手性丙氨酸酯引入1,8-萘二酸酐结构中,接着通过钯催化的Sonogashira反应合成了新型的1,8-萘酰亚胺结构的芘荧光化合物,并研究了它们在四氢呋喃溶液和聚集态的圆二色吸收和圆偏振发光性质。该手性分子在四氢呋喃溶液中的圆二色吸收和圆偏振发光信号是静默的,而其在聚集态下能够通过π-π相互作用自组装成螺旋纳米纤维,并展示出了强的镜面对映的科顿效应和圆偏振发光信号。
[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.
【学位授予单位】：南京大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：TQ422

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