共轭型二苯甲酮染料的合成与双光子性质的研究.pdf

共轭型二苯甲酮染料的合成与双光子性质的研究.pdf重庆大学硕士学位论文共轭型二苯甲酮染料的合成与双光子性质的研究姓名:王建超申请学位级别:硕士专业:化学指导教师:高放2010-04中文摘要I 摘要由于共轭型双光子染料的化学结构易于修饰,光学性质可控,光物理与光化学性质的可调节性强,因而受到人们的广泛关注。为实现在分子水平上调控双光子光引发聚合的目标,可通过提高电子给体与电子受体的强度或提高共轭中心母体的平面性来增大化合物的双光子吸收截面。据此,我们构建了共轭双键连接紫外光引发剂的双光子染料,通过改变苯乙烯的取代基团,设计合成了九种含二苯甲酮的苯乙烯类化合物,重点研究了这些新型共轭型二苯甲酮化合物的光谱及双光子性质。本文研究的主要内容和结果如下:1. 合成了九种新的目标化合物,并通过熔点、1HNMR谱、MR谱、质谱及元素分析进行了表征。2. 研究了化合物在不同溶剂中紫外可见吸收与荧光发射。光谱中在短波长区的吸收主要由二苯甲酮片段提供,而可见光区的吸收是由分子内电荷转移引起的,随着苯乙烯上的取代基的供吸电子能力的不同,化合物具有不同的分子内电荷转移能力。全面系统地分析,考察了溶剂、结构变化对光谱性质的影响。用荧光比较法测定了荧光量子产率,并检测了目标化合物的荧光寿命。3. 研究了化合物的双光子吸收性质。测定了化合物的双光子上转换荧光,并用荧光比较法计算了化合物的双光子吸收截面,结果表明,五种化合物皆具有明显的上转换荧光发射,其双光子吸收横截面的大小与二苯甲酮取代位置表现出一定的相关性。4. 对共轭型二苯甲酮光引发剂的电化学行为、热稳定性进行了研究,并对目标化合物进行了分子构型优化计算。发现前线轨道能量与分子的电子密度分布及取代位置均有一定依赖关系。关键词:二苯甲酮衍生物,双光子聚合,双光子吸收截面,电化学,分子结构优化英文摘要III ABSTRACT Conjugated two-photon dyes have drawn of the increasing interests of people,as they can be modified easily, controllable in optical properties, and adjustable in photophysical and photochemical properties. In order to achieve two-photon polymerization at the molecular level, people try to increase two-photon absorption cross section by improving electron donor and electron acceptor strength and improving the planarity of the π-conjugated matrix. We constructed two-photon dyes with the conjugated double bonds connecting two-photon UV initiator dye and changing the substituent groups of styrene, We synthesized nine styrene derivatives containing benzophenone segment and their spectra and two-photon properties of these pounds was investigated. The main research contents and results are as following: 1. Nine new pounds were synthesized, and pounds were characterized by the melting point, 1HNMR, MR, mass spectrum and elemental analysis. 2. UV-visible absorption and fluorescence emission were detected in various solvents. Absorption in the short wavelength region is mainly caused by benzophenone segment; absorption in the visible wavelength region is due to the intramolecular electron transfer. Different substituents on styr