论文总字数：30674字

摘 要

多金属氧酸盐因为它们的结构多样性和在磁性，催化，电化学，气体储存/分离等领域的多功能应用，在过去几十年中已经广泛应用于晶体工程中，以建立有机-无机杂化复合物。本论文中主要从多酸阴离子出发，选用Y型1，3,5-三（1-咪唑基）苯（1,3,5-tris(1-imidazoly)benzene, 简写为tib）作为有机配体，在水热条件下，获得了两个新的基于Keggin型多酸和含氮配体的无机-有机杂化化合物：[Ni₂(tib)₂(H₂O)₄(a-SiW₁₂O₄₀)]﹒6H2O(1)和[Co₂(tib)₂(H₂O)₄(a-SiW₁₂O₄₀)]﹒6H2O (2)。本文中通过单晶X射线衍射，红外光谱，热重分析，粉末X射线衍射等对这两个化合物的结构进行了表征，同时对于这两个化合物的催化和三阶非线性光学性质进行了探索研究。单晶结构分析表明化合物1和2都是三维超分子结构，它们的主体部分都是由金属-tib配合物阳离子与多酸阴离子组成的。值得注意的是，化合物1和2的结构中都存在着环-连接-环的金属-有机配体链。据我们所知，已报道的由tib合成的多为配位聚合物，化合物1和2是少有的由tib修饰的多酸化合物。此外，Z-扫描测试表明，化合物1和2都是具有较好的双光子吸收截面的新型无机-有机复合材料，在三阶非线性光学材料领域有着良好的潜在应用。

关键词: 多金属氧酸盐，含氮配体，非线性光学

The Design, Synthesis and Functional Properties of Novel Polyoxometalates Modified by

ABSTRACT

Polyoxometalates (POMs), possessing structural diversity and versatile applications in areas such as magnetism, catalysis, electrochemistry, gas storage/separation, and so on, and have been extensively used in crystal engineering to build organic–inorganic hybrid complexes during the past decades. In this thesis, two novel inorganic-organic hybrid compounds based on POMs and N-heterocycle ligands, formulated as [Ni₂(tib)₂(H₂O)₄(a-SiW₁₂O₄₀)]﹒6H2O (1) and [Co₂(tib)₂(H₂O)₄(a-SiW₁₂O₄₀)]﹒6H2O (2)， were successfully synthesized by employing Y-shaped organic ligands 1,3,5-tris(1-imidazoly)benzene (abbreviated as tib) under hydrothermal conditions. And they were characterized by single crystal X-ray diffraction (Single crystal XRD), infrared spectra (IR), thermal gravimetric (TG) analysis and powder X-ray diffraction (PXRD). Additionally, the catalytic and nonlinear optical (NLO) properties of these compounds were also investigated.

Single crystal X-ray structure analysis showed compounds 1 and 2 are three-dimensional supramolecular structures, and their main part is composed of metal-tib complex cation and polyoxoanion. It is worth noting that both the circle-connecting-circle metal-organic ligand chains are present in the structures of compounds 1 and 2. As far as we know, most reported compounds synthesized by tib are polymers, while compounds 1 and 2 are tib-modified polyoxomelate compounds. In addition, Z-scan shows that compounds 1 and 2 are novel inorganic-organic hybrid materials with good two-photon absorption cross-section, and have a good potential application in the field of third-order nonlinear optical materials.

KEYWORDS: Polyoxometalates; N-heterocycle ligand; Nonlinear Optics

目 录

摘 要 I

ABSTRACT II

第一章 文献综述 1

1.1 多酸化学简介 1

1.2 多酸化合物的合成方法 2

1.3 多酸化学的应用 3

1.3.1 多酸在催化领域的应用 3

1.3.2 多酸在药物化学领域的应用 4

1.3.3 多酸在材料化学领域的应用 5

1.4 多酸修饰的研究进展 6

1.5 本课题研究的目的及内容 8

第二章 实验部分 10

2.1 实验试剂和测试仪器 10

2.1.1 实验试剂 10

2.1.2 测试仪器 10

2.2 合成实验 11

2.2.1 α- 9-硅钨酸盐的合成 11

2.2.2 tib配体的合成 11

2.2.3 化合物1的合成 12

2.2.4 化合物2的合成 12

第三章 结果与讨论 13

3.1 晶体结构 13

3.1.1 单晶X射线衍射数据 13

3.1.2 化合物1的晶体结构 15

3.1.3 化合物2的晶体结构 17

3.2 表征与性质 18

3.2.1 红外光谱 18

3.2.2 粉末X射线衍射 19

3.2.3 热重分析 20

3.2.4 催化性质 20

3.2.5 双光子吸收 25

第四章 结论与展望 27

4.1 结论 27

4.2 展望 27

参考文献 28

致谢 33

第一章 文献综述

1.1多金属氧酸盐化学研究的进展简介

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