摘 要

多金属氧酸盐（POMs）是由金属、氧原子连接形成的簇合物，因其独特的结构及性质，在光学，材料，磁性，催化以及生物医药等方面具有良好的应用前景，备受科研工作者的青睐。近年来，通过有机配体修饰无机多酸离子，从而实现有机-无机组分之间的功能互补已经成为多酸化学研究的热点。本文主要采用水热合成技术，以过渡金属为结点，构建共轭有机配体与多酸相结合的新型功能材料。通过调节pH值，温度，反应时间和初始反应物等条件，成功合成了3个NTB(NTB = 三(2-苯并咪唑甲基)胺)修饰的多酸基无机-有机复合物：(C₅NH₅)₄[Co(NTB)]₂[Co(H₉P₄Mo₆O₃₁)₂]·6H₂O (1)，(C₅NH₅)₄[Cd(C₅NH₅)]₂[Cd(NTB))]₂[Cd(H₇P₄Mo₆O₃₁)₂]·6H₂O (2)，(C₂H₆O)₂(C₅NH₅)₅[ZnO][Zn(C₅NH₅)][Zn(NTB))]₂[Zn(H₈P₄Mo₆O₃₁)₂]·6H₂O (3)。并通过单晶X-射线衍射，红外光谱，粉末XRD等手段进行化合物结构的表征。结构分析表明，化合物(1)包含两个[P₄Mo₆O₃₁]^6-阴离子，两个NTB配体、三个Co离子、4个吡啶分子和6个晶格水。化合物(2)的结构与化合物(1)类似，不同的是化合物(2)还包含两个连有吡啶分子的Cd。化合物(3)的主要结构单元中存在两个[P₄Mo₆O₃₁]^6-阴离子，.2个NTB配体、6个吡啶分子、5个Zn离子、2个乙酸根分子以及6个晶格水。此外，对化合物的三阶非线性等性质进行了研究。

关键词：多金属氧酸盐 共轭有机配体 三阶非线性光学

Synthesis and Functional Properties of Novel Inorganic-Organic Composite Materials Based on Polyoxometalates Modified by Conjugated Organtic Ligands

Abstract

Polyoxometalates (POMs) is a kind of important metal cluster constructed by metal and oxygen atoms. Recently, POMs have aroused increasing attention not only because of their unmatched structural versatility, but importantly owing to their numerous potential applications in magnetism, nonlinear optics, materials, catalysis and medicine. In recent years, a research hot spot has been arised in the POMs chemistry, which the organic ligands modify inorganic polyoxoanions to realize the functional complement of organic and inorganic components. We utilize transition metal as the connection point, constructing novel functional materials connected by conjugated organic ligands and POMs. In this thesis, three non-reported inorganic-organic hybrid compounds based on POMs and modified by NTB have been successfully synthesized under hydrothermal conditions by means of controlling the pH value, temperature, reaction time and initial reactant and so on：(C₅NH₅)₄[Co(NTB)]₂[Co(H₉P₄Mo₆O₃₁)₂]·6H₂O (1), (C₅NH₅)₄[Cd(C₅NH₅)]₂[Cd(NTB))]₂[Cd(H₇P₄Mo₆O₃₁)₂]·6H₂O (2), (C₂H₅O)₂(C₅NH₅)₅[ZnO][Zn(C₅NH₅)][Zn(NTB))]₂[Zn(H₈P₄Mo₆O₃₁)₂]·6H₂O (3)。And the structure of the compound was characterized by single crystal X-ray diffraction, infrared spectroscopy, powder XRD. Structural analysis reveals that compound (1) contain two [P₄Mo₆O₃₁] ^6- anion, two NTB ligands, three Co ions, four pyridine molecules and six lattice water. The structure of compound (2) is similar to that of compound (1), except that compound (2）also contains two Cd molecules with pyridine molecules,. There are two [P₄Mo₆O₃₁] ^6- anions, two NTB ligands, six pyridine molecules, five Zn ions, two acetate molecules and six lattice water in the main structural units of the compound (3). Additionally, nonlinear optical (NLO) was also investigated.

Key Words: Polyoxometalates; Conjugated organic ligands; Third-order nonlinear optical

目 录

摘要………………………………………………………………………………………………I

Abstract…………………………………………………………………………………………II

第一章 文献综述 1

1.1 多酸化学的发展 1

1.2 多酸化学的前沿和热点 2

1.2.1 支撑型有机修饰多酸的研究 3

1.2.2 高核化多酸的研究 3

1.2.3 多维多孔化多酸的研究 4

1.3多酸化学的应用 6

1.3.1 多酸的催化化学 6

1.3.2 多酸的电池中的应用 8

1.3.3 多酸的药物方面的应用 9

1.3.4 多酸的绿色化学方面的应用 9

1.4选题思想和意义 11

第二章 M-NTB配合物修饰的多酸基无机-有机杂化材料的合成 12

2.1 仪器与试剂 12

2.1.1 试剂 12

2.1.2 测试手段 12

2.2 单晶培养 13

2.2.1 (C₅NH₅)₄[Co(NTB)]₂[Co(H₉P₄Mo₆O₃₁)₂]·6H₂O (1)的合成 13

2.2.2 (C₅NH₅)₄[Cd(C₅NH₅)]₂[Cd(NTB))]₂[Cd(H₇P₄Mo₆O₃₁)₂]·6H₂O (2)的合成 13

2.2.3 (C₂H₅O)₂(C₅NH₅)₅[ZnO][Zn(C₅NH₅)][Zn(NTB))]₂[Zn(H₈P₄Mo₆O₃₁)₂]·6H₂O (3) 的合成 13

第三章 结果与讨论 14

3.1 引言 14

3.2 晶体结构 14

3.2.1 (C₅NH₅)₄[Co(NTB)]₂[Co(P₉Mo₆O₃₁)₂]·6H₂O (1)的晶体结构 16

3.2.2 (C₅NH₅)₄[Cd(C₅NH₅)]₂[Cd(NTB))]₂[Cd(H₇P₄Mo₆O₃₁)₂]·6H₂O (2)的晶体结构. 18

3.2.3 (C₂H₅O)₂(C₅NH₅)₅[ZnO][Zn(C₅NH₅)][Zn(NTB))]₂[Zn(H₈P₄Mo₆O₃₁)₂]·6H₂O (3)的晶体结构 21

3.3 表征与性质 23

3.3.1 红外光谱 23

3.3.2 X-射线粉末衍射 24

3.3.3 双光子吸收 26

3.4 本章小结 28

第四章 结论与展望 31

参考文献 32

致谢........................................................................................................................37

第一章 文献综述

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