臺灣博碩士論文加值系統

本論文主要以含氫氧基修飾之咪唑基為中心，與不同金屬配位後產生金屬液晶化合物，進而研究並探討其液晶特性。其中包括(1)含銀(I)，金(I)及鈀(II)之咪唑基金屬化合物，(2)含銀(I),金(I)之金屬碳烯化合物，(3)含金(III)陰離子之咪唑鹽類與奈米複合材料。

Metallomesogens of the types (i) N-(2-hydroxyl)alkyl imidazole coordinated with Silver(I), Gold(I), and Palladium(II) ions (in Chapter II), (ii) Silver(I) and Gold(I) complexes of N-hexadecanyl-N´-(2-hydroxyhexadecanyl) imidazol-2-ylidenes (in Chapter III), and (iii) nanocomposites of Gold nanoparticles embedded in N,N´-di-substituted imidazolium salt (in Chapter IV) are presented. The characterizations, results, and discussions are described in each section.

TABLES OF CONTENTS i
LIST OF SCHEMES v
LIST OF TABLES vi
LIST OF FIGURES vii
Chapter I. Introduction 1
Chapter II. A Pendant 2-Hydroxyl Group Induced Liquid Crystal and Structural Transformation. Silver(I), Gold(I), and Palladium(II) Complexes of N-(2-ydroxyl)alkyl Imidazoles. 5
Abstract 5
Introduction 5
Synthesis of metal-imidazole complexes 7
Neutral versus ionic Au(I) complexes 8
Single crystal structures 9
Structure of [Ag(C10(2-OH)-im)2][NO3] 10
Structure of [Au(C6(2-OH)-im)Cl] 12
Structure of [Pd(C6(2-OH)-im)2Cl2] 14
Liquid crystalline properties 16
Ionic Ag(I) complexes, [Ag(Cn(2-OH)-im)2][X], X = NO3, BF4, and PF6 18
Ionic Au(I) complexes, [Au(Cn(2-OH)-im)2][X], X = NO3, BF4, and PF6 19
Neutral Au(I) complexes, [Au(Cn(2-OH)-im)Cl] 21
Neutral Pd(II) complexes, [Pd(Cn(2-OH)-im)2Cl2] 21
Powder X-ray diffraction studies 23
Ag-imidazole complexes, [Ag(Cn(2-OH)-im)2][X], X = NO3, BF4, and PF6 24
Ionic Au-imidazole complexes, [Au(Cn(2-OH)-im)2][X], X = NO3, BF4, and PF6 25
Neutral Au-imidazole complexes, [Au(Cn(2-OH)-im)Cl] 25
Neutral Pd-imidazole complexes, [Pd(Cn(2-OH)-im)2Cl2] 26
FT-IR spectroscopy 27
Metal nanostructures 28
Structural transformation 30
Conclusions 32
Chapter III. Hydroxyl Group Functionalized N-heterocyclic Carbene Complexes of Silver(I) and Gold(I). Hydroggen-bonding and Aurophilicity Induced Mesophase. 35
Abstract 35
Introduction 35
Synthesis and characterization 38
Nuclear Magnetic Resonance (NMR) spectrum studies 39
Single crystal structure of [(Ag(C16,C16(2-OH)-imy)2)2][Ag2Cl4] 44
Liquid crystalline properties 46
Imidazolium salts, [C16,C16(2-OH)-im][X] X = Cl, BF4, and PF6 46
Ag(I) NHC, [(Ag(C16,C16(2-OH)-imy)2)2][Ag2Cl4] 47
Au(I) NHC, [Au(C16,C16(2-OH)-imy)Cl] 50
Au(I) NHCs, [Au(C16,C16(2-OH)-imy)2][X], X = BF4, PF6 53
Photophysical properties 55
Synthesis of nanomaterials 57
Conclusions 60

Chapter IV. Composites of Gold Nanoparticles Embedded in Liquid Crystalline Imidazolium Salts. An Unusual Temperature Depended Surface Plasmon Resonance Behavior and Structural Transformation. 61
Abstract 61
Introduction 61
Synthesis of imidazolium tetrachloroaurate salts 63
Single crystal structures 64
[C16,C16-im][AuCl4], 1 64
[C12,C12(2-OH)-im][AuCl4], 3 65
Gold nanoparticles and nanocomposites 68
Prepared from compound 1 69
Prepared form compound 3 81
Prepared form tetrahexadecylammonium bromide (THAB) 84
Conclusions 86
Chapter V. Experiment Sections 87
General Information 87
Synthesis of Chapter II. 89
Bis(1-(2-hydroxy)alkylimidazole) silver(I) complexes 89
Bis(1-(2-hydroxy)alkylimidazole) gold(I) complexes 91
1-(2-hydroxy)alkylimidazole gold(I) chloride 94
Dichlorobis(1-(2-hydroxy)alkylimidazole) palladium(II) complexes 97
Synthesis of Chapter III. 99
1-(2-hydroxyhexadecanyl)-3-hexadecanylimidazole chloride, [C16,C16(2-OH)-im][Cl] 99
1-(2-hydroxyhexadecanyl)-3-hexadecanylimidazole tetrafluoroborate / hexafluorophosphate, [C16,C16(2-OH)-im][BF4] / [C16,C16(2-OH)-im][PF6] 100
Bis(1-(2-hydroxyhexadecanyl)-3-hexadecanylimidazolin-2-ylidene)silver(I) chloride, [Ag(C16,C16(2-OH)-im)2][Ag2Cl4] 101
(1-(2-hydroxyhexadecanyl)-3-hexadecanylimidazolin-2-ylidene)gold(I) chloride, [Au(C16,C16(2-OH)-im)Cl] 102
Bis(1-(2-hydroxyhexadecanyl)-3-hexadecanylimidazolin-2-ylidene)gold(I) tetrafluoroborate / hexafluorophosphate, [Au(C16,C16(2-OH)-im)2][BF4] and [Au(C16,C16(2-OH)-im)2][PF6] 103
Synthesis of Chapter IV. 104
1,3-dihexadecyl-imidazolium tetrachloroaurate, [C16,C16-im][AuCl4] (1) 105
1-(2-hydroxyhexadecanyl)-3-hexadecanylimidazole tetrachloroaurate, [C16,C16(2-OH)-im][AuCl4] (2) 105
1-(2-hydroxydodecanyl)-3-dodecanylimidazole tetrachloroaurate, [C12,C12(2-OH)-im][AuCl4] (3) 105
Chapter VI. References 107

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