论文总字数：41989字

摘 要

多金属氧酸盐，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，因此，备受研究工作者的青睐。本文采用溶剂热合成法，通过调节反应时间、温度、原料、溶剂配比等反应条件，成功合成了三种无机-有机杂化材料：[(L-C₄O₆H₂)₂V₄O₈]·2C₆N₂H₁₈（化合物1）、[(D-C₄O₆H₂)₂V₄O₈]·2C₆N₂H₁₈（化合物2）、(C₂N₂H₈)₂(C₆NOH₆)₂V₆O₈(CH₃O)₆（化合物3），并借助单晶X-射线衍射、红外、粉末X-射线衍射、元素分析、热重分析等手段进行了表征。另外，初步探索了部分化合物的三阶非线性光学性能。主要内容概括如下：

分别使用两种对映异构体（L-酒石酸和D-酒石酸）作为配体合成了两种基于V₄O₈建筑结构单元的有机-无机杂化材料：[(L-C₄O₆H₂)₂V₄O₈]·2C₆N₂H₁₈（化合物1）和[(D-C₄O₆H₂)₂V₄O₈]·2C₆N₂H₁₈（化合物2）。单晶X-射线衍射表明：两种化合物均呈现手性且互为镜面对称。由于存在质子化的游离的四甲基乙二胺，各个{V₄}氧簇通过游离在四周的有机胺离子形成氢键相互连接，进而形成了三维超分子结构。通过开孔Z-扫描发现：化合物1、2都具有双光子吸收效应。另外，使用邻氨基苯酚和乙二胺为配体并置于甲醇环境中反应，制得一种新颖的{V₆}多钒酸盐：(C₂N₂H₈)₂(C₆NOH₆)₂V₆O₈(CH₃O)₆（化合物3）。其中所有的钒原子都是六配位的，形成了八面体结构。在这种多钒酸盐中，相邻的{V₆}簇通过三个氢键相互连接，从而形成了三维的超分子结构。

关键词：多金属钒酸盐 溶剂热合成 手性 三阶非线性光学

Synthesis and Properties of Functional Composites Based on Polyoxovanadates

Abstract

Recently, Polyoxometalates (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 this thesis, three non-reported compounds based on POMs have been successfully synthesized under hydrothermal conditions by means of controlling the reaction time, temperature, and initial reactant and so on. The structures of compounds were characterized by single crystal X-ray diffraction (Single crystal XRD), infrared spectra (IR) and powder X-ray diffraction (PXRD). Additionally, the nonlinear optical (NLO) properties of some compounds were also investigated. The main contents are included as follow:

Two kinds of organic-inorganic compounds based on V₄O₈ building structural units were synthesized using two enantiomers (L-tartaric acid and D-tartaric acid) as ligands:[(L-C₄O₆H₂)₂V₄O₈]·2C₆N₂H₁₈(Compound 1) and [(D-C₄O₆H₂)₂V₄O₈]·2C₆N₂H₁₈(Compound 2). Single crystal X-ray diffraction shows that both compounds exhibit chirality and mirror symmetry. Due to the presence of protonated free tetramethylethylenediamine, each {V4} oxygen cluster is connected to each other by the formation of hydrogen bonds in the surrounding organic amine ions, thereby forming a three-dimensional supramolecular structure. Through the Z-scan, it is found that both compounds 1 and 2 have a two-photon absorption effect. In addition, a new type of POVs-(C₂N₂H₈)₂(C₆NOH₆)₂V₆O₈(CH₃O)₆ (Compound 3)-were prepared by the use of O-aminophenol and ethylenediamine as a ligand and placed in the methanol environment. Wherein all of the vanadium atoms are hexacoordinated to form a octahedral structure, but different mutual coordination environments. In this POVs, the adjacent {V6} clusters are connected to each other by three hydrogen bonds, resulting in a three-dimensional supramolecular structure.

KEYWORDS: Polyoxovanadates; Solvothermalsynthesis; Chirality; Third-order nonlinear optical

目录

摘要 I

Abstract II

第一章 文献综述 1

1.1 多金属氧酸盐化学的发展历史 1

1.2 多酸化学的前沿和热点 3

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

1.3 多金属氧酸盐的合成 3

1.4 多金属氧酸盐的应用 4

1.4.1 在催化领域的应用 4

1.4.2 在生命医药领域的应用 7

1.4.3 在材料化学领域的应用 7

1.5 多钒金属氧酸盐的研究现状 7

1.5.1 高核多钒酸盐 9

1.5.2 多钒酸盐的修饰化 9

1.5.3 混合价态或还原态的多钒酸盐 11

1.6 论文选题思路 12

1.7 仪器与测试 13

1.7.1 测试仪器 13

1.7.2 化学试剂 13

第二章 多钒酸盐的有机配体修饰和性质表征 14

2.1 引言 14

2.2 单晶培养 14

2.2.1 [(L-C₄O₆H₂)₂V₄O₈]·C₆N₂H₁₆ (1)的合成 14

2.2.2 [(D-C₄O₆H₂)₂V₄O₈]·C₆N₂H₁₆ (2)的合成 14

2.2.3 (C₂N₂H₈)₂(C₆NOH₆)₂V₆O₈(CH₃O)₆(3)的合成 15

2.3 晶体结构解析 15

2.3.1 X-射线晶体学衍射数据 15

2.3.2 [(L-C₄O₆H₂)₂V₄O₈]·2C₆N₂H₁₈ (1)的晶体结构 16

2.3.3 [(D-C₄O₆H₂)₂V₄O₈]·2C₆N₂H₁₈ (2)的晶体结构 18

2.3.3 (C₂N₂H₈)₂(C₆NOH₆)₂V₆O₈(CH₃O)₆(3)晶体结构 19

2.4 性质表征 20

2.4.1 粉末X-射线衍射分析 20

2.4.2 红外光谱 22

2.4.2 CD光谱 and价键计算 23

2.4.3 热重分析 24

2.4.4 双光子吸收 25

2.5 本章小结 27

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