【作者】 袁光辉；

【导师】 薛冬峰；

【作者基本信息】 大连理工大学 ， 化学工艺， 2007， 硕士

【摘要】 硼酸盐化合物以其丰富的结构类型和优异的性能被广泛用作激光材料、发光基质材料尤其是非线性光学晶体材料，因此一直是广大学者关注的热点。硼酸盐晶体中，硼原子可采用两种杂化方式与氧原子键合：平面三角形的sp²杂化[Bφ₃]和四面体形的sp³杂化[Bφ₄](φ=O^2-，OH^-)。[Bφ₃]和[Bφ₄]基团共用顶点（氧原子）连接形成刚性的硼氧聚阴离子基团，这些基团是晶体结构中的阴离子重复单元，即基本结构单元（FBB）。FBB再缩合或多聚形成岛状孤立基团、一维无穷链状基团、二维无穷层状基团和三维无穷骨架状基团，从而形成了丰富多彩的硼酸盐晶体的结构类型。本文主要以无机晶体结构数据库（ICSD，2004）为数据来源（2004年以后的新型硼酸盐数据来自相关文献），借助Diamond和Mercury等软件对所有可用的硼酸盐进行了结构分析和统计研究。主要研究结论：1．把硼酸盐中的FBB按照其拓扑结构不同分成了单个Bφ₃或Bφ₄ FBB、枝状FBB、普环FBB、桥环FBB、螺环FBB和复合环FBB六种类型。2．提出了一种新的更直观易用的代数描述法用以描述硼酸盐FBB的拓扑结构及它们在晶体结构中的排布。3．依据FBB自身的拓扑结构不同和在晶体结构中的排布方式不同（孤立、成链、成层、成三维网架）对所有可用的硼酸盐进行了系统的分类。4．硼酸盐及硼磷酸盐的结构主要来自聚阴离子的影响，A代硼酸盐（M_xB_yA_z）中，A的电负性越大，B的共价配位数越高。5．硼酸盐和硼磷酸盐不仅有丰富的结构和独特的结构特征，而且非中心对称化合物占有较高的比例，是探索新的非线性光学晶体材料很好的搜索源。更多还原

【Abstract】 On the basis of their abundant structures, borates are widely used as laser materials,luminescence host materials and non-linear optical materials, and have therefore attractedconsiderable attention.In borate crystals, the boron atoms are hybridized forming sp² structures with trigonalsymmetry [Bφ₃] or sp³ structures exhibiting tetrahedral symmetry [Bφ₄] (φ=O^2-, OH^-). These[Bφ₃] and [Bφ₄] polyhedra can be connected via common comers （oxygen atoms） to formrigid boron-oxygen groups. These groups represent the anionic repeat units of the crystalstructures and are called fundamental building blocks （FBBs）. The FBBs can polymerize intocomplex borate polyanions such as infinite chains, layers and framework anions. Therefore,borates have the abundant structures. In this paper, we take the Inorganic Crystal StructureDatabase （ICSD, 2004） as data source and analyze all available borate structures by dint ofDiamond and Mercury softwares. The conclusions of the paper show:1. The fundamental building blocks of all available borates can be divided into 6 types:single Bφ₃ or Bφ₄ FBB, branched FBB, normal-ring FBB, bridge-ring FBB, helical-ring FBBand combined-ring FBB.2. A simpler and convenient algebraic description is proposed to describe the topologicalstructure of FBBs and their polymerization in borates.3. On the basis of the topological structure of FBB and their polymerization in borates（isolate, chain, layer and framework）, a new systematic borate-classification is put forward,and all available borates are classified.4. The structures of borates and borophosphates are primarily influenced by polyanions,and in borates M_xB_yA_z the number of coordination of B atoms increases with theelectronegativity of A atoms.5. Based on the abundant characteristic structures and the high percentage ofnon-centrosymmetric compounds, borates and porophosphstes are the good field to search fornew non-linear optical materials.更多还原