平面铝配合物的化学键特征及含DTE双金属钌配合物二阶非线性光学性质调控的计算研究

发布时间：2018-08-30 07:37

【摘要】：金属铝配合物因其独有的结构和成键特点被广泛应用于材料科学领域。金属铝配合物具有平面构型,金属铝与配体成键时由于没有d电子的参与,其配位键特性与过渡金属配合物不同,深入研究金属铝与配体间的成键特点具有重要科学意义。另外,含DTE的双金属钌乙烯基配合物在材料领域上备受瞩目而且具有很大的应用空间。通过取代基效应和DTE基团的可逆性光异构化性质对该类配合物的非线性光学(NLO)性质进行调控并使之具有优良的NLO效应。通过理论计算可为设计更具潜力的非线性光学材料提供理论依据和指导。本论文应用量子化学计算方法探究平面金属铝配合物的化学键特征和光学性质及含DTE双金属钌乙炔基配合物的二阶非线性光学性质,主要研究工作有:(1)采用密度泛函理论研究了平面构型的配合物1[(PhI2P2-)AlCl],2[(PhI2P2-)GaCl]和3[(PhI2P2-)NiCl]。结果表明,金属M(M=Al,Ga,Ni)和配体L(PhI2P2-)之间的作用不是典型的两电子三中心作用而是一种静电和共价键的混合作用。通过定域化轨道指示函数,电子定域函数,能量分解证明M和L之间的作用存在的共价键成分的特征。同时,利用含时密度泛函理论对配合物1-3的吸收光谱进行了模拟。吸收光谱图显示配合物3相对配合物1,2出现了红移现象。在分子水平上对键之间的相互作用的研究有利于更好地设计和合成这样的平面构型配合物。(2)采用密度泛函理论对含DTE的双金属钌乙烯基配合物光异构化过程的二阶NLO性质进行研究。计算结果表明,第一超极化率随着配体π共轭程度增加和供电子能力增强而逐渐增大,并且DTE基团可通过光刺激作用几何结构发生可逆变化,在光可切换过程中发挥重要作用。光异构化过程使得这些配合物的二阶NLO性质得到明显调控。因此,这些结果对于深入探讨具有二阶NLO开关效应的配合物提供理论参考和研究方法。
[Abstract]:Metal aluminum complexes are widely used in material science due to their unique structure and bonding characteristics. The metal aluminum complex has a planar configuration and its coordination bond characteristics are different from that of the transition metal complex due to the absence of d electrons in the bonding between the metal aluminum and the ligand. It is of great scientific significance to further study the bonding characteristics between the metal aluminum and the ligand. In addition, bimetallic ruthenium vinyl complexes containing DTE have attracted much attention in the field of materials and have great application space. The nonlinear optical (NLO) properties of the complexes are regulated by the substituent effect and the reversible photoisomerization property of the DTE group and the excellent NLO effect is obtained. Theoretical calculation can provide theoretical basis and guidance for the design of nonlinear optical materials with more potential. In this paper, the chemical bond characteristics and optical properties of planar aluminum complexes and the second-order nonlinear optical properties of DTE bimetallic ruthenium acetynyl complexes are investigated by quantum chemical calculation. The main works are as follows: (1) the planar complexes 1 [(PhI2P2-) AlCl] 2 [(PhI2P2-) GaCl] and 3 [(PhI2P2-) NiCl] have been studied by density functional theory. The results show that the interaction between metal M and ligand L (PhI2P2-) is not a typical two-electron three-center interaction but a mixture of electrostatic and covalent bonds. By localizing the orbital indicator function, the electron localizing function and the energy decomposition, the characteristics of the covalent bond components of the interaction between M and L are proved. At the same time, the absorption spectra of complexes 1-3 were simulated by time-dependent density functional theory. The absorption spectra showed that the red shift of complex 3 was observed in relation to complex 1 and 2. The study of bond interaction at molecular level is beneficial to the better design and synthesis of such planar complexes. (2) density functional Theory (DFT) is used to study the photoisomerization process of ruthenium vinyl complexes containing DTE. The order NLO property is studied. The results show that the first hyperpolarizability increases gradually with the increase of 蟺 conjugation degree of ligand and the enhancement of electron donor ability, and the DTE group can play an important role in the optically switchable process by reversible changes in the geometrical structure of the photostimuli. The second order NLO properties of these complexes are obviously regulated by the photoisomerization process. Therefore, these results provide a theoretical reference and research method for the further study of complexes with second-order NLO switching effect.
【学位授予单位】：东北师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4

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