臺灣博碩士論文加值系統

成功以有機官能機將多金屬氧簇官能基化合成具有多重功能之新穎複合材料，具亞銨基之多金屬氧簇在近年是科學家們研究的對象，使用DCC及苯銨可以成功開發出許多含有亞苯銨多金屬氧簇，像是Lindqvist 六鉬酸衍生物。
八鉬酸氧簇與苯銨可以在溫和的條件下進行加成反應，以N,N-二環己基碳二亞胺做脫水劑，可以成功將苯銨加成上八鉬酸氧簇合成出多金屬氧簇 [(n-C4H9)4N]2[Mo6O17(NAr)2] (Ar = 2,6-C6H4Cl2)，使用紫外光吸收光譜儀、氫譜核磁共振儀、ESI質譜儀、傅立葉紅外光譜儀及元素分析儀鑑定後，可以得知共加成上六鉬酸氧簇兩個苯銨取代基 (2.6-dichloroaniline)。

Functionalization of polyoxometalates with organic groups to generate new species has attracted much interest to generate new hybrid materials towards various fascinating applications. Organoimido derivatized polyoxometalates (POMs) is one of topics in recent years. A great number of arylimido derivatives including polymers of the Lindqvist hexamolybdate clusters by reaction with aromatic amines and DCC have been succesfully developed .
The reaction of octamolybdate [Mo8O26]4- with aromatic amines can easily take place under much milder conditions. A novel functionalization by attaching aromatic amines to polyoxometalates [(n-C4H9)4N]2[Mo6O17(NAr)2] (Ar = 2,6-C6H4Cl2) has been successfully performed by a reaction of octamolybdate with 2,6-dichloroaniline with N,N’ dicyclocarbodiimide, as a dehydrating agent. This compound has been characterized by UV-Vis, 1H-NMR, ESI MS, FTIR, and Elemental Analysis. The results indicated bi-functional of aromatic amino groups (2.6-dichloroaniline) on the hexamolybdate cluster.

ABSTRACT iv
ACKNOWLEDGEMENT v
CONTENTS............................................................................................................vi
LIST OF FIGURE ix
LIST OF TABLE xi
CHAPTER 1-INTRODUCTION 1
I.1. General Challenge 1
I.2. Polyoxometalates 2
1.3.Functionalization Polyoxometalates 6
1.4.Organoimido Derivatives Lindqvist Hexamolybdate Cluster 7
1.5.Research Objective 13
1.6.Outline 14
CHAPTER II-EXPERIMENTAL 15
2.1. General Procedure 15
2.2. Synthesis Tetrabutylammonium Hexamolybdate 16
2.3. Synthesis Tetrabutylammonium Octamolybdate 17
2.4. Synthesis Tetrabutylammonium Hexamolybdate – 2.6 dichloroaniline 18

2.5. Purification Method 19
2.5.1. Solvent Extraction 19
2.5.2. Column Chromatography 21
2.5.3. Crystallization 23
CHAPTER 3-RESULT AND DISCUSSION 25
3.1. Synthesis 25
3.2. UV-Visible Spectroscopy 27
3.2.1. UV Visible Spectroscopy Tetrabutylammonium Hexamolybdate 28
3.2.2. UV Visible Spectroscopy Tetrabutylammonium Octamolybdate 30
3.2.3. UV Visible Spectroscopy Tetrabutylammonium Hexamolybdate-2,6-dichloroaniline [(n-C4H9)4N]2 [Mo6O17(N-2.6-C6H4Cl2)2] 32
3.3. 1H-NMR 33
3.3.1. 1H-NMR Tetrabutylammonium Hexamolybdate 34
3.3.1. 1H-NMR Tetrabutylammonium Octamolybdate 36
3.3.3. 1H-NMR TBA Hexamolybdate -2.6,dichloroaniline 37
3.4. IR Spectroscopy 39
3.4.1. IR Spectroscopy Tetrabutylammonium Hexamolybdate 45
3.4.2. IR Spectroscopy Tetrabutylammonium Octamolybdate 41
3.4.3. IR Spectroscopy Tetrabutylammonium Hexamolybdate – 2.6-
dichloroaniline [(n-C4H9)4N]2 [Mo6O17 (N–2.6-C6H4Cl2)2] 42
3.5. Hexamolybdate and Octamolybdate Structure........................................44
3.6. Conversion from Octamolybdate to Hexamolybdate 2,6-dichloroaniline.........................................................................................48
CHAPTER 4 CONCLUSION 50
REFERENCE 52
UV Result A1
IR Spectroscopy Result A3
1H-NMR A6
ESI MS (Nanospray) A9
Element Analysis [(n-C4H9)4N]2 [Mo6O17 (N-2.6-C6H4Cl2)2].................... A12

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