含重金属离子的芳香炔低聚物的合成及其性质研究

发布时间：2018-06-30 01:54

本文选题：芳香炔低聚物 + 非线性光学特性　；参考：《郑州大学》2016年硕士论文

【摘要】：芳香铂炔类低聚物含有重金属离子和大的π电子共轭体系,是近年来研究较多的一种非线性光学材料。根据文献报道,包含有推拉电子结构的小分子共轭化合物一般具有一定程度的双光子吸收特性,而含有重金属离子的配合物一般具有较大的反饱和吸收特性。我们设计合成了一类含有重金属离子的芳香铂或汞的炔类低聚物,在化合物的两端引入相同或不同结构的推拉电子基团,以期得到同时具有双光子吸收和反饱和吸收特性的非线性光学材料。本论文首先利用Sonogashira反应,以碘化亚铜、Pd(PPh3)2Cl2和三苯基膦做催化剂合成出芳香炔的中间体,再利用经典的Hagihara偶合反应得到七种含有不同官能团的铂或汞芳香低聚物。利用核磁共振氢谱、碳谱、磷谱以及元素分析、质谱等实验技术对其结构进行了表征。目标化合物的紫外吸收特征光谱的波长在259~394 nm范围内,这主要是化合物中配体的π-π*跃迁的特征吸收,随着化合物共轭体系的增加和两端取代基推拉电子能力的增加,π电子的离域能力增强,化合物的最大吸收发生红移。目标化合物的荧光光谱的发射波长在328~496 nm范围内,当化合物的共轭体系增大时,荧光光谱也发生红移。我们利用溶致变色法测定了目标化合物的一阶超极化率的范围在1.56×10-29~3.16×10-28 cm5/esu。从测试数据完了可以得出,重金属离子的引入,增强了化合物的一级超极化率;当化合物共轭体系相同时,取代基的给电子能力越强,化合物分子的一阶超极化率越大;化合物的共轭体系增大,相应的一阶超极化率也就越大;两端取代基具有推拉电子特性的化合物,其一级超极化率也就越大。此外我们还用Gaussian03程序在B3LYP水平上对目标化合物的分子轨道进行计算。计算结果表明,随着芳香体系的增大,金属的dπ轨道对HOMO轨道的贡献也相对减弱。
[Abstract]:Aromatic platinum alkynes oligomers contain heavy metal ions and large 蟺 electron conjugation systems, which are widely studied as nonlinear optical materials in recent years. According to the literature, small molecular conjugated compounds with push-pull electron structure generally have a certain degree of two-photon absorption, while complexes containing heavy metal ions generally have a large anti-saturation absorption characteristics. We have designed and synthesized a class of aromatic platinum or mercury oligomers containing heavy metal ions, and introduced the same or different structure push-pull electron groups at both ends of the compounds. The nonlinear optical materials with two photon absorption and anti-saturation absorption can be obtained. In this paper, the intermediates of aromatic acetylene were synthesized by Sonogashira reaction using cuprous iodide Pd (PPh3) 2Cl2 and triphenylphosphine as catalysts. Seven kinds of aromatic oligomers containing different functional groups of platinum or mercury were obtained by classical Hagihara coupling reaction. The structure was characterized by nuclear magnetic resonance spectroscopy, carbon spectrum, phosphorus spectrum, elemental analysis and mass spectrometry. The UV absorption characteristic spectrum of the target compound is in the range of 259 ~ 394 nm, which is mainly the characteristic absorption of 蟺-蟺 * transition of ligand in the compound. With the increase of conjugation system and the ability of the two end substituents to push and pull electrons, the delocalization ability of 蟺 electrons is enhanced, and the maximum absorption of the compounds is red-shifted. The emission wavelength of the fluorescence spectrum of the target compound is in the range of 328N 496 nm. When the conjugated system of the compound increases, the fluorescence spectrum also shows a red shift. We have determined the first order hyperpolarizability of the target compound in the range of 1.56 脳 10-293.16 脳 10-28 cm5 / Eu by discoloration method. It can be concluded from the test data that the introduction of heavy metal ions enhances the first-order hyperpolarizability of the compounds, and the stronger the electron feeding ability of the substituents is, the greater the first-order hyperpolarizability of the compounds is when the conjugation system is the same. The higher the conjugated system is, the greater the first order hyperpolarizability of the compounds is, and the higher the first order hyperpolarizability of the compounds with the push-pull electron properties of the substituents is. In addition, the molecular orbitals of the target compounds are calculated at the B3LYP level by Gaussian03 program. The calculated results show that with the increase of aromatic system, the contribution of the d 蟺 orbital of metal to Homo orbital is relatively weakened.
【学位授予单位】：郑州大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O631

【相似文献】