【作者】 黄招辉；

【导师】 郭丰启；

【作者基本信息】 郑州大学 ， 物理化学， 2013， 硕士

【摘要】 铂芳香炔低聚物是近几年研究比较多的一类新型重金属芳香炔类低聚物,这类物质包含了铂乙炔结构单元和大的电子共轭系统,这为其提供了一些独特的光物理性能,特别是在非线性光学材料方面展现出优良的应用前景。过渡金属离子的d轨道和共轭π电子的自旋-耦合轨道作用使含有重金属离子和刚性结构的分子能够表现出大的反饱和吸收特性。本论文选择了铂炔类化合物作为研究对象,合成了一系列含有给-受体结构的三支链铂芳香炔共轭低聚物(1-6)。利用元素分析、核磁共振氢谱、质谱等技术手段对它们的结构进行了表征。对所有目标化合物的紫外-可见吸收光谱特性、荧光和荧光量子产率、反饱和吸收和一阶超极化率进行了初步研究。三嗪为中心的配合物(1-3)的最大吸收相对于三苯胺为中心的配合物(4-6)的最大吸收红移38-40nm。配合物4-6在空气饱和的氯仿溶液中的发射光谱显示两个主要发射峰。其中具有更短的波长的峰归因于它们的荧光,具有较长的波长的峰归因于他们的磷光。然而,化合物1～3在空气饱和的氯仿溶液中只检测到了荧光。用溶致变色法测定了6个目标化合物的分子的一阶超极化率在4.06×10-29～2.11×10-28cm5/esu范围,比一些常见的非线性光学的材料的一阶超极化率高出很多。利用开孔Z-扫描技术对目标化合物的非线性吸收特性进行了测试,结果表明化合物2和5表现出良好的非线性光学性能,化合物1～6的σeff/σo的值在2-22之间,σeff->σ0,说明了这类化合物具有比较好的反饱和吸收特征。更多还原

【Abstract】 Platinum acetylides are a new type of heavy metal aromatic alkynes that have been researched intensively in recent years. The heavy metallic ion and the large π-conjugated systems confer these organometallic oligomers great unique properties, especially the great nonlinear optical property. Molecules containing heavy metal ions and rigid structures always exhibit large reverse saturable absorption due to the spin-orbit coupling between the d orbital of the transition metal ion and the conjugate π electron, which can enhance their reverse saturable absorption properties greatly.In this thesis, a series of conjugated platinum (II) acetylide complexes with multi-branched donor-acceptor structures (1-6) were synthesized. The target products were characterized via elemental analysis,’HNMR, MS, etc., respectively.The UV-vis absorption spectra, luminescence spectra, fluorescence quantum yields, and phosphorescence quantum yields of these complexes1-6were tested. Finally the nonlinear absorption and the first order hyperpolarizability were measured using open aperture Z-scan technique and solvatochromic method, respectively. The absorption maxima of the triazine-centered complexes (1-3) are38-40nm red-shifted compared to those of the triphenylamine-centered complexes (4～6). The luminescence spectra of the complexes4-6in air-saturated chloroform showed two main emission peaks, in which the peak with shorter wavelength was ascribed to their fluorescence, and the peak with longer wavelength was ascribed to their phosphorescence. However, only the fluorescence has been detected for1～3in air-saturated chloroform. The molecular first order hyperpolarizabilities of the six target compounds were tested using solvatochromic method, and their molecular hyperpolarizabilities are in the range of4.06×10-29～2.11×10-28cm5/esu, which is much higher than that of some other common nonlinear optical materials. The results indicated that complexes2and5exhibit excellent nonlinear absorption properties. The ratios of the effective nonlinear absorption cross section to ground-state absorption cross section σeff/σ0of complexes1～6are in the range of4～22, aeffis far bigger than σ0, which indicates that this kind of compounds has the characteristics of the saturated absorption.更多还原