非心结构硼酸铅及稀土硼酸盐的设计合成及光电性能的研究

Second-order nonlinear optical materials are of great current interest due to their practical application in such fields as national defense, communications and research, so it is necessary for the rational design and syntheses of novel second-order nonlinear optical crystalline materials: Based on the theory that the synergistic effect between B-O groups and acentric metal-oxygen polyhedrons (Ln-O polyhedrons; Pb-O polyhedrons containing the 6s2 lone pair of electrons) may offer greater opportunities to form acentric compound, we use alkali metals, alkaline earth metals or organic amines as structure-directing agents to design and synthesis novel acentric heterometallic borate crystal materials under one- or muti-step hydro(solvo)thermal conditions. Subsequently, their structures and properties are characterized systematically, especially their second-order nonlinear optical properties and ferroelectric properties are also studied. In addition, we summarize the relationship between the reaction conditions and the structures of desired products, and mainly focus on that the effects on the structures when the synthesis and crystallization of products are carried out respectively, or the starting reactants are introduced into the reaction system at different times. Furthermore, we also explore the connection between the product structures and their photoelectric properties, particularly discuss the adjustment and modification of various acentric building blocks as well as their self-assemble modes may induce the formation of desired acentric structures in detail. In a word, all these not only provide us basic services to exploit and develop second-order nonlinear optical materials, but also accumulate experience for the structural design and controllable synthesis of functional materials.

根据国防、通讯、科研等领域的需求，合成新型二阶非线性光学晶体材料：通过一步或多步水（溶剂）热合成方法，以碱金属，碱土金属或有机胺为结构导向剂，利用三配位硼氧单元和非心的金属氧多面体（稀土氧多面体；含6s2孤对电子的铅氧多面体）协同作用提高非心化合物形成的几率，设计合成具有非心结构的异金属硼酸盐晶体材料。对其结构和性能进行系统的测试和表征，重点研究其二阶非线性光学性能和铁电性能。总结反应条件与产物结构的关系，侧重研究物质合成与产品晶化分步进行，反应物分步引入,两种方法对结构的影响。探索产物结构与光电性能之间的联系，主要研究各种非心结构建筑单元及其自组装模式对二阶非线性光学性能的影响。进而从理论上勾画理想的空间构型。再通过对建筑单元的调整和修饰，诱导其自组装形成理想的目标结构。为二阶非线性光学材料的开发与研制作提供基础性服务，为功能材料的结构设计与可控合成积累经验。

根据国防、通讯、科研等领域的需求，合成新型二阶非线性光学晶体材料：通过一步或多步水（溶剂）热合成方法，以碱金属，碱土金属或有机胺为结构导向剂，利用三配位硼氧单元和非心的金属氧多面体（稀土氧多面体；含6s2孤对电子的铅氧多面体）协同作用提高非心化合物形成的几率，设计合成具有非心结构的异金属硼酸盐晶体材料。对其结构和性能进行系统的测试和表征，重点研究其二阶非线性光学性能。获得并报道了一系列碱金属，碱土金属或有机胺为模板剂的硼酸盐，硼酸铝以及硼酸铅化合物，其中一些化合物具有优良的非线性光学性能。获得了一例不具备非线性光学性能的稀土硼酸盐，相关工作正在整理。上述工作为二阶非线性光学材料的开发与研制作提供了基础性服务，为功能材料的结构设计与可控合成积累了经验。. 同时，还尝试将硼酸盐和多金属氧簇（缺位Kiggin多酸和稀土有机锗簇）结合。成功的将硼酸引入缺位多酸体系，相关工作正在深入研究。虽然没有将硼酸引入稀土有机锗体系，但是在硼酸存在时，我们合成了一系列新颖的稀土有机锗化合物，可能具有良好的磁学性能，相关测试正在进行。