【作者】 刘继红；

【导师】 刘波；

【作者基本信息】 哈尔滨理工大学 ， 材料学， 2013， 博士

【摘要】 为了解决“非线性-透光性矛盾”，运用“分子工程”和“晶体工程”理论，设计合成了几种吡啶盐类非线性光学材料。用红外、核磁共振氢谱、核磁共振碳谱、元素分析、质谱、紫外-可见光谱和荧光光谱等对其结构和性能进行了表征。依据双能级模型，选用合适的溶致变色方程，测定了分子的二阶极化率，并对测定过程进行了详细阐述。结果表明这些材料分子具有较大的二阶极化率，并有较好的透光性。“非线性-透光性矛盾”的协调解决取决于共轭链的长度、电子给体和电子受体的选择以及二维电荷转移结构的设计等分子综合优化设计思路。论文的主要工作包括：设计、合成一系列吡啶盐类有机非线性光学材料；利用元素分析、红外光谱和核磁共振等测试手段进行结构表征；研究吡啶盐类有机非线性光学分子的紫外-可见光谱和荧光光谱，采用溶致变色法测定分子二阶非线性极化率；对有机非线性光学分子二阶非线性极化率与分子结构的关系进行研究讨论。具体展开了以下几个方面的研究工作：1.设计合成具有一维电荷转移结构的D-π-A型含咪唑环的吡啶盐类NLO材料：ISPI、ISPT、ISSPI和ISSPT，这些材料分子均为新化合物。2.用对甲苯磺酸根离子替换碘离子，得到两个阴离子系列的吡啶盐类NLO材料。3.设计合成具有二维电荷转移结构的A-π-D-π-A型含咔唑环的吡啶盐类NLO材料：3,6-CVPI和1,8-CVPI，其中1,8-CVPI是新化合物。4.对上述吡啶盐类有机NLO材料的合成路线进行了合理的设计，对部分合成方法做了适当的改进。改进后的合成方法反应速度更快，产率更高，产品更加纯净。另外对改进方法的反应条件进行了优化。5.利用元素分析、红外光谱、核磁共振氢谱和核磁共振碳谱等现代分析测试手段对所合成的吡啶盐类有机非线性光学材料进行了结构表征。6.采用溶剂自然挥发晶体生长法培养出吡啶盐单晶，用X-射线单晶衍射仪测定其晶体结构。7.研究吡啶盐类NLO分子在不同极性溶剂中的荧光发射光谱和紫外-可见吸收光谱，用溶致变色法测算出几种吡啶盐的分子二阶非线性极化率(β)。这些吡啶盐类有机NLO材料同时拥有较大的分子二阶非线性极化率和较好的透明性，实现了“非线性-透明性”的均衡统一。更多还原

【Abstract】 Several nonlinear optical pyridiniums were designed and synthesized tobalance the nonlinearity-transparency trade-off by molecular engineering theoryand crystal engineering theory. The pyridiniums were characterized by IR,1HNMR,13C NMR, MS, UV-Vis and fluorescence spectra. The second-orderpolarizability of the chromophores was determined by a solvatochromic methodbased on two-level model. The chromophores have large second-orderpolarizability and exthibit good transparency. The nonlinearity-transparencytrade-off is due to the two-dimensional structure, the choice of electron acceptors,electron donors and the conjugation length.The main task of this dissertation includes the following research works:designing and synthesizing a series of pyridiniums nonlinear optical organicmaterial, determining the structures of the pyridiniums by test means such aselementary analysis, infrared spectrum and nuclear magnetic resonance,measuring molecular second-order nonlinear polarizabilities by solvatochromismmethod, and discussing the relationship between molecular structures andsecond-order nonlinear polarizabilities (β) of the pyridiniums. Main researchworks are as follows:1. New pyridiniums NLO materials with one-dimensional D-π-A structure aredesigned and synthesized. They are ISPI, ISPT, ISSPI and ISSPT.2. The tosylate ions are replaced with the iodine ions to obtain two series ofpyridiniums NLO materials with different anions.3. Two two-dimentional A-π-D-π-A pyridiniums NLO materials with carbazolyare designed and synthesized. They are3,6-CVPI and1,8-CVPI.4. Synthetic routes to the target pyridiniums NLO materials are designedreasonably. Some synthetic methods are improved appropriately. The improvedreactions have faster speed, higher yield and purer products. In addition, reaction conditions of the improved reactions are optimized.5. The structures of the pyridiniums NLO materials are characterized withmodern test means such as elementary analysis, infrared spectrum,1H-nuclearmagnetic resonance and13C-nuclear magnetic resonance.6. Single crystals of pyridiniums are produced by crystal grown method ofslow solvent evaporation. The crystal structures are determined by X-Ray singlecrystal diffraction.7. The UV-vis absorption spectra and the fluorescence emission spectra of thepyridiniums NLO materials are studied. The second-order polarizabilities of thepyridiniums are determined by solvatochromic method. These pyridiniums NLOmaterials have higher second-order polarizabilities and better transparency, andexhibit excellent nonlinearity-transparency trade-off.更多还原