【作者】 李莉；

【导师】 孙思修；

【作者基本信息】 山东大学 ， 无机化学， 2009， 博士

【摘要】 1961年,Franken首次发现了水晶激光倍频现象。这一现象的发现,不仅标志着非线性光学的诞生,而且强有力地促进了非线性光学晶体材料的迅速发展。随着非线性光学的深入研究和新型材料的不断发展,使得非线性光学晶体材料在信息通讯、激光二极管、图像处理、光信号处理及光计算等众多领域都具有极为重要的作用和巨大的潜在应用,这些研究与应用对非线性光学晶体又提出了更多更高的物理化学性能要求,同时许多应用也还在层出不穷地发展之中,正是由于非线性光学晶体有着如此广阔的应用前景以及这些应用可能带来的光电子技术领域的重大突破,所以寻找与合成性能优异的新型非线性光学晶体一直是一个非常重要的课题,成为该领域人们关注的热点之一。总的来说非线性光学的主要研究内容包括两方面:一是发现新的非线性光学现象,揭示它们的机理和规律,发展非线性光学新技术和新材料。另一方面则是把非线性光学效应与技术应用到相关领域。金属-有机配合物是近二十年才发现的一类新型的半有机非线性光学材料,它同时兼有无机材料和有机材料的优点,如具有较大的非线性光学系数、短的紫外截止波长、稳定的物理化学性质、高的非线性光学系数、结构多样性和可裁剪性等特点。金属-有机配合物的中心金属原子或离子不仅可以充当电子施主和受主,还可以充当连接电子施主和受主的桥梁,通过改变金属有机配合物中心金属离子或配体,可以有效地调控、优化配合物的物理化学性质,并可提高晶体材料的加工处理能力。因此,金属-有机配合物成为具有很好应用前景的一类非线性光学晶体。本论文主要以有机磷配体三苯基氧化磷（TPPO）作为起始原料,在温和条件下,设计、合成了一系列金属-有机配合物,测定其晶体结构,并积极开展了一些相关的物理化学性质的研究,努力揭示晶体结构与其二阶非线性光学效应之间的新现象,新问题,为进一步拓展和深化该工作奠定基础。本论文研究的主要内容及创新点:1)将有机磷配体TPPO引入二阶非线性光学晶体材料的合成中,合成了一系列ⅡB族金属与TPPO的配合物ZnCl₂（TPPO）₂（1）、ZnBr₂（TPPO）₂（2）ZnI₂（TPPO）₂（3）、CdCl₂（TPPO）₂（4）和HgBr₂（TPPO）₂（5）,测定了其晶体结构、粉末倍频效应以及透过光谱。结果表明,晶体（1）、（2）、（3）和（5）为非中心对称结构,晶体（1）的粉末倍频效应最强,约为KDP的4倍,（2）、（3）、（5）的粉末倍频效应则依次减弱,其中（3）和（5）的粉末倍频效应大约和KDP的相同。将粉末倍频效应较强的（1）生长出了大块单晶,并测得其转换效率为1.5%,光损伤阈值为～2.4 GW/cm²。转换效率高于KDP,而且可实现相位匹配。（1）的某些性能优于KDP,可望应用于实际。2)将共轭配体NCS^-引入TPPO与ⅡB族金属离子体系中,在温和条件下合成了配合物Zn（NCS）₂（TPPO）₂（6）、[Cd（NCS）₂（TPPO）]_n（7）和[Zn（TPPO）₄][Zn（NCS）₃（TPPO）]₂（8）。其中（6）和（7）为中心对称结构,没有倍频效应,（8）为非中心对称结构,其粉末显示较弱的倍频效应,约为KDP的0.5倍。3)在温和条件下合成了对氨基苯甲酸桥连的配位聚合物[Zn（PABA）₂]·H₂O（9）、[Zn（H₂O）₂（H₂PO₄）₂]·2PABA（10）和PABA·H₃PO₄（11）。测定了其晶体结构,其中只有（9）为非中心对称结构,其粉末倍频强度约大约与KDP相同。当晶体（9）受热失去其空穴中的水分子后,其倍频效应几乎消失了,究其原因,可能是由于空穴中的水分子与对氨基苯甲酸配体形成的分子间氢键对整个化合物的倍频效应有比较大的贡献,当失去水分子后,这种分子间氢键也就不存在了,所以倍频效应也随之消失了。有趣的是,水分子又可以很快的返回到空穴当中,当又吸水后其粉末倍频强度也恢复了。（10）和（11）都为对氨基苯甲酸支撑的层状有机.无机杂化聚合物。（10）的特点在于其结构中包含了ZnO₆八面体,而（11）的特点在于它是一个由分子间氢键作用联系的无机酸和有机酸交替排列的杂化聚合物。4)在温和条件下合成了稀土元素La、Ce、Pr和Nd与配体TPPO和phen的10配位、零维配合物。在相同条件下用Nd以后的重稀土Sm、Eu和Gd等合成,则都没有成功,这可能是因为镧系收缩效应所致。随着原子数增加,镧系原子半径逐渐减小,而配体TPPO和phen的空间位阻都比较大所以难以生成配合物。更多还原

【Abstract】 The first second harmonic generation（SHG） phenomenon was discovered in 1961 use quartz with Cr:Al₂O₃ by Franken.It not only symbolized the naissance of the nonlinear optic science,also accelerated the development of the nonlinear optical crystal forcefully.Along with the deep research in the nonlinear optic science and the continuous development of the new materials,nonlinear optical crystal materials have the important potential applications in telecommunications,optical computing,laser diode,optical signal processing,and optic data storage.These research and applications bring forward more requests for the physical and chemical properties of nonlinear optical crystals.At the same time,many applications are developing endlessly.Therefore,search and synthesize new type of nonlinear optical crystal with excellent properties is a very important task.Also,it becomes a focus for many scientists in this field.The research on the nonlinear optics includes two aspects.One is discover new nonlinear optic phenomena,find out their mechanism and rule and develop new nonlinear optic technique and materials.The other is to apply nonlinear optic technique into the relative fields.Metal-organic complex is new type of semi-organic nonlinear optical materials that were discovered in the latest two decades.Metal-organic complex can combine the advantages of both organic and inorganic materials,such as high NLO efficiency,low cut-off wavelength,various and flexible of structure,and stable physical and chemical properties.In metal-organic complex,the central mental ions can act as electron acceptor,donor,or the bridge connects the donor and acceptor.The physical and chemical properties of the complex can be effectively dominated by changing the central ions and ligand.Consequently,metal-organic complex is a very promising nonlinear optical crystal.In this dissertation,we chose some simple ligands as raw materials.A series of metal-organic complex were synthesized under room temperature.Their molecule structures were determined and some relative physical and chemical properties were studied in the purpose of discovering some new phenomena between the structure and NLO properties.It will settle foundation studies for developing this work frothily.The main works in this dissertation are list as follows:（1） TPPO was introduced into the synthesis of the second order nonlinear optic crystal materials.A series of complex containⅡB group metal and TPPO were synthesized.Their formula were determined as ZnCl₂（TPPO）₂（1）,ZnBr₂（TPPO）₂（2）, ZnI₂（TPPO）₂（3）,CdCl₂（TPPO）₂（4） and HgBr₂（TPPO）₂（5）.The frequency-doubling effects and transmittance spectrum were measured.The results indicate that the frequency-doubling effect of crystal（1） is most intensity in all of these five crystals. The powder SHG intensity of（1） was estimated about 4 times that of KDP.The powder SHG intensity of（2）,（3） and（5） were decreased in turn.Big crystal of（1） was grown under room temperature.The conversion efficiency and threshold were measured to be 1.5%and～2.4 GW/cm².Some properties of（1） are superior to that of KDP.More importantly,the crystal of（1）can reach phase matching of SHG in the visible region.Therefore,it appears to be a promising candidate for fabricating NLO frequency conversion devices.（2） In this chapter,NCS^- was introduced into the system of TPPO andⅡB group complex.Zn（NCS）₂（TPPO）₂（6）,[Cd（NCS）₂（TPPO）]_n（7） and [Zn（TPPO）₄][Zn（NCS）₃（TPPO）]₂（8） were synthesized under room temperature and their structure were determined.Only（8） has a noncentrosymmetry configuration. Powder SHG intensity of（8） was estimated about 0.5 time that of KDP.（3） p-Aminobenzoic acid pillared coordinated polymer[Zn（PABA）₂]·H₂O（9）, [Zn（H₂O）₂（H₂PO₄）₂]·2PABA（10） and PABA·H₃PO₄（11） were synthsizied under room temperature,and their structure were determined.Only（9） has a noncentrosymmetry configuration.The powder SHG efficiency of（9） is comparable with that of KDP. Furthermore,the SHG efficiency of compound（9） after removal and reintroduction of the guest H₂O molecules were measured.The SHG efficiency is decreased obviously after removal of the guest H₂O molecules.And it can come back when the H₂O molecules were reintroduced into the framework.This can be attributed to the two following reasons.（a） When the H₂O molecules were removed,the relative positions of some atoms in the crystal lattice may be changed to a certain extent.（b） The hydrogen bonding between H₂O molecules and carboxylic oxygen atoms may have more contribution to the SHG efficiency.So,the SHG efficiency decreased with the removal of the H₂O molecules.（10） and（11） are 3D supramolecular hybrid complex pillared by PABA ligand.The structure of（10） was featured by containing ZnO₆ octahedral,and（11） was a hybrid complex constructed from alternately arranged organic acid and inorganic acid layers.（4） In this chapter,a series of zero dimensional complex Ln（phen）（TPPO）₂（NO₃）₃ （Ln=La,Ce,Pr,Nd） were synthesized under room temperature.We tried to synthesize the complex using heavy rare earth ions after Nd,but failed.We think it was controlled by lanthanide contraction effect.更多还原