新型无机硼酸盐的结构设计与物化性能

To synthesize borogermanates, borosilicates, antimony（III）-borates and boroselenites of alkali, alkaline earth，lanthanide and transition metal ions by high temperature solid state reactions or hydrothermal reactions; to introduce d0-transition metal MO6 distorted octahedra or lone pair containing cations such as Pb(II) and Bi(III) into the above systems so as to obtain new types of Second Harmonic Generation (SHG) crystals by additive polarizations from two types of asymmetric structural groups; to summarize the effects of synthetic conditions, the size of counter-cations, nature and the packing patterns of these asymmetric structural building units on the SHG properties of above inorganic solids through a great number of synthetic experiments, physical property measurements and theoretical calculations; to design and synthsize one to two candidates of new SHG crystals for further studies and future applications. SHG materials have wide applications in laser and optical communications, this research project involves many branches of sciences such as structure chemistry, solid state chemistry and materials chemistry, hence this study is very important to both basic reseach and applications of new high-tech crystal materials. . Upon the completion of this research project, about 8-10 research papers will be published in improtant chemistry journals including JACS and Angew. Chem. In. Ed. and 2 to 3 patents will be applied.

以高温固相反应或水热合成方法合成碱金属、碱土金属、稀土或过渡金属的硼锗（或硅）酸盐、亚硒（或锑）硼酸盐等, 在上述体系中引入d0-过渡金属MO6畸变八面体或含孤对电子的Pb(II)或Bi（III）等阳离子, 利用两种不对称结构基团的协同极化效应诱导非中心对称结构的形成而获得到性能优良的新型硼酸盐二阶非线性光学晶体; 通过大量的合成实验、性能测试及理论计算, 总结上述硼酸盐固体化合物的二阶非线性光学性能随合成条件、抗衡阳离子大小、不对称结构单元的性质及其排列与组装方式的调控规律; 设计合成一到两种性能优越的新型硼酸盐二阶非线性光学晶体备选材料。 非线性光学材料在激光及光通讯领域有广泛的应用, 本项目研究属结构化学、固体化学及材料化学等交叉科学, 对于新晶体材料的基础研究与及开发应用均有非常重要意义。。在包括JACS，Angew Chem In Ed 等国际核心学术刊物上发表8-10 篇左右学术论文，申请专利2 至3 项。

硼酸盐晶体在非线性光学晶体中占有非常重要的地位， 简单硼酸盐已经被挖掘得很充分了，对硼酸盐衍生物的研究可以发现新型硼酸盐NLO晶体。在本项目中我们对新型硼酸盐及其衍生物体系进行了较为系统的研究工作， 得到了多种结构新颖的新型硼酸盐化合物如硼酸-硝酸盐、硼锑酸盐、硼酸-羧酸盐等， 其中不少化合物具有非中心对称结构， 有些化合物表现出优异的二阶非线性光学性能， 如Pb2(BO3)(NO3)表现出9倍于KDP的二阶非线性光学效应等。 本项目取得的研究结果为新型硼酸盐化合物的设计合成打下了坚实的基础。 在Angew. Chem. Int. Ed., J. Amer. Chem. Soc., Chem. Eur. J., Inorg. Chem., Dalton Trans., CrystEngcommun.等重要化学刊物发表标注论文22篇， 获得5项专利授权。培养博士毕业生4名，硕士毕业生2名。

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