邻位碳硼烷衍生物氧化还原和二阶NLO性质的DFT研究

发布时间：2018-01-10 09:11

本文关键词：邻位碳硼烷衍生物氧化还原和二阶NLO性质的DFT研究　出处：《东北师范大学》2016年硕士论文　论文类型：学位论文

【摘要】：非线性光学(NLO)过程由于在各种光电调节器如光学通信、数据操作、存储和传输等方面的应用在理论和实验上备受关注。二十面体碳硼烷和金属碳硼烷由于具有刚性结构,在有机溶剂中的高溶解性等特点,近年来这类体系的电子结构、成键特征和NLO性质成为理论和实验研究的热点之一。本论文采用密度泛函理论(DFT)方法计算了12顶点碳硼烷及金属钌碳硼烷的二阶NLO性质,主要工作有：(1)采用DFT方法对四氟碳硼烷及其衍生物的结构和NLO性质进行了计算讨论。结果表明,改变四氟碳硼烷上部取代基的共轭性或在碳硼笼下部引入强的吸电子基,会使碳硼笼扩张或收缩。取代基的体积大小和共轭性是影响极化率、第一超极化率值的主要因素。碳硼笼上部取代基的给受电子能力越强其偶极矩越大,如四硝基碳硼烷的碳硼笼中引入强吸电子其基偶极矩增大。碳硼笼到具有良好共轭性的并苯的电荷转移增加了二阶NLO响应。(2)采用DFT方法研究一系列具有2,2'-联吡啶和碘离子配体的12顶点钌碳硼烷夹心配合物。计算表明配合物的第一超极化率(βtot)随着取代基电子供体2,2'-联毗啶和碘离子取代-CO基而增大。取代基增加βtot值主要是配体内电荷转移,配体到金属电荷转移和钌离子的d-d跃迁的贡献。对于配合物3,发生氧化还原后配合物的βtot值减少,配合物4的氧化过程减小βtot。值,而它的还原过程βtot值增加。可见,不同的取代基和氧化还原过程显著影响12顶点钌碳硼烷体系的NLO响应。
[Abstract]:Nonlinear Optical NLOs (NLOs) process data operations due to various optoelectronic regulators such as optical communication. The applications of storage and transport have attracted much attention in theory and experiment. 20 hedron carboborane and metal carboborane have the characteristics of rigid structure and high solubility in organic solvents. The electronic structure of such systems in recent years. Bonding characteristics and NLO properties have become one of the hot topics in theory and experiment. In this paper, the second-order NLO properties of 12-vertex carboborane and ruthenium carboborane are calculated by density functional theory (DFT). The structure and NLO properties of tetrafluorocarborane and its derivatives were calculated and discussed by DFT method. Changing the conjugation of the upper substituent of tetrafluorocarbon-borane or introducing a strong electron-absorbing group into the lower part of the carbon-boron cage will cause the expansion or contraction of the carbon-boron cage. The volume and conjugation of the substituents affect the polarizability. The higher the electron capacity, the greater the dipole moment of the superpolarizability of the upper carbon boron cage. For example, in the carbon boron cage of tetranitrocarbon borane, the base dipole moment of the strong electron absorber is increased. The charge transfer from the carbon boron cage to benzene with good conjugation property increases the second order NLO response. DFT method was used to study a series of 2. The results show that the first hyperpolarizability (尾 totn) of the complexes is with the substituent electron donor 2. The increase of 尾 tot was mainly due to the charge transfer in ligands. The contribution of ligand to metal charge transfer and d-d transition of ruthenium ion. For complex 3, the 尾 tot value of complex decreases after redox and the oxidation process of complex 4 decreases 尾. However, the 尾 tot value increased during the reduction process. It can be seen that different substituents and redox processes significantly affect the NLO response of ruthenium carboborane system with 12 vertices.
【学位授予单位】：东北师范大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O641;O437

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