非心金属硼硅酸盐的设计合成及其非线性光学性能的研究

The exploration of new non-linear optical (NLO) materials with excellent performance is premised on the effective design and synthesis of non-centrosymmetrical compounds. Borates are attracting increasing attentions due to their preference to present as non-centrosymmetrical structural characterization. The presented project is to synthesize novel metal borosilicates with non-centrasymmetrical structures. The construction of such structural features is based on the synergistic combination of non-symmetrical BxOy clusters and rigid SiO4 tetrahedron, and the structure-directing cations with asymmetric coordination environment (i.e. alkali metal ion, alkali earth metal ion), or with lone-pair of electrons (i.e. Pb2+, Bi3+). We will explore the reaction temperature, period and solvents under hydro(solvo)thermal conditions with various silicon and boron sources. A detailed comparison will be carried out about the effect of different oxo-boron clusters and cations with different coordination environments on the structures. Furthermore, systematical secondary order non-linear optical measurements will be performed on these materials to explore the relationship between structure and property. Besides, we will probe for the reaction conditions of step method to synthesize borate compounds, providing an experimental playground for the synthesis novel borate-based non-linear optical materials. This project will develop structure chemistry, coordination chemistry and non-linear optics, possessing important scientific significance.

有效的设计和合成具有非心结构的化合物，是获得性能优异的非线性光学材料的前提。在无机化合物中，硼酸盐易于呈现出非心结构的特性，从而受到人们的关注。本项目拟在水热/溶剂热条件下，利用具有不对称配位环境的碱（土）金属或具有孤对电子的Pb2+、Bi3+金属阳离子作为结构导向剂,通过非心结构的硼氧簇与刚性SiO4四面体的协同组合，以不同的硼源与硅源作为原料，探索合适的反应温度、反应周期和溶剂，合成具有非心结构的金属硼硅酸盐，总结合成的条件与规律，研究所得化合物的结构与热稳定性，考察不同的非心硼氧簇和不对称配位环境的阳离子对化合物结构的影响。并进行系统的二阶非线性光学性质研究，探讨构效关系。此外，探索分步合成法在硼酸盐化合物中的反应条件，为新型硼酸盐基非线性光学晶体的合成提供实验基础。本项目将推动结构化学、配位化学以及非线性光学的发展，具有重要的科学意义。

硼酸盐因其丰富的结构和优异的光学性能，受到化学、材料等领域科研工作者的广泛关注。我们对硼酸盐及其衍生物等体系的合成中进行了大量的探索，通过一步水热（溶剂热）合成方法，以有机胺、碱金属阳离子和过渡金属配合物为结构导向剂，成功合成出一系列金属硼酸盐，并对其结构和性能进行了系统的测试和表征，重点研究了其中具有非心结构的化合物的二阶非线性光学性能。这些化合物丰富了硼酸盐的结构化学，为非线性光学材料的结构设计与可控合成积累了经验。相关研究成果已经在Inorganic Chemistry等国际学术期刊发表。