Design of functionalised ligands and metal complexes for self-assembly at the liquid, solid interface [Elektronische Ressource] : STM-visualisation of 2D-nano-patterns / vorgelegt von Philipp Zell

Phil Richardson

Informations

• Publié par: universitat_ulm
• Publié le: 01 janvier 2005
• Nombre de lectures: 20
• Langue: English
• Poids de l'ouvrage: 18 Mo

Extrait

Universität Ulm

Anorganische Chemie II

Materialien und Katalyse



Design of
Functionalised Ligands and Metal Complexes
for Self-Assembly at the Liquid/Solid Interface

STM-Visualisation of 2D Nano-Patterns


Dissertation
zur Erlangung des Doktorgrades Dr. rer. nat.
der Fakultät für Naturwissenschaften
der Universität Ulm


vorgelegt von

Philipp Zell
aus
Biberach/Riss


2005













































Amtierender Dekan: Prof. Dr. K.-D. Spindler
1. Gutachter: Prof. Dr. B. Rieger
2. Dr. D. Volkmer
Tag der Promotion: 27. Juni 2006









Als ob Kunst nicht auch Natur wäre,
und Natur Kunst!
Christian Morgenstern (1871 - 1914)




Kunst (Escher)

Natur (SAMs)


















Contents


1 Introduction 1
1.1 Nanotechnology – a key technology 1
1.1.1 Background and milestones of Nanotechnology 2
1.1.2 Nanotechnology – one word, many technologies 3
1.2 Trend in catalysis 7
1.3 Motivation and aim of the thesis 9
1.4 References 11
2 STM on 2D Nano-Patterns of Defined Metal Complexes 15
2.1 Microscopy on atomic scale 15
2.2 STM-studies on 2D self-assembled metal complexes 18
2.2.1 SAMs by chemisorption 18
2.2.2 Langmuir-Blodgett monolayers 20
2.2.3 Vapour deposition in UHV 21
2.2.4 Self-assembly at the liquid/solid interface 24
2.2.5 In situ electrochemical STM 29
2.2.6 Comparison of the methods 30
2.3 References 31
3 Experimental Background 35
4 STM-Visualisation of Functionalised Bis-imine Ligands 41
4.1 Introduction 41
4.2 Syntheses of alkoxy substituted bis-imine ligands 45
4.3 Pyridine bis-imine Pd(II) complexes 48
4.4 STM investigations 50
4.4.1 Pyridine bis-imine ligands 50
4.4.2 Isophthal bis-imine ligand 53
i 4.5 Conclusion 55
4.6 Experimental section 56
4.6.1 Syntheses of the starting materials 56
4.6.2 Bis-imine ligands 58
4.6.3 Pd(II) complexes 60
4.7 References 61
5 Fine-Tuning in 2D − Bis-Salicylaldehydato/-aldiminato Complexes 63
5.1 Introduction 63
5.2 Functionalised bis-salicylaldehydato/-aldiminato M(II) complexes 66
5.2.1 Free alkoxy substituted salicylaldehyde ligands 66
5.2.2 Bis-salicylaldehydato M(II) complexes 67
5.2.3 Bis-salicylaldiminato (N-H) M(II) complexes 68
5.2.4 Tetra-substituted bis-salicylaldiminato M(II) complexes 69
5.2 STM investigations 72
5.2.1 Pattern type 1 − bis-salicylaldehydato M(II) complexes 72
5.2.2 Pattern type 2 − bis-salicylaldiminato (N-H) M(II) complexes 82
5.3.3 Secondary 2D-modification of a bis-salicylaldiminato (N-H) Cu(II) complex 85
5.3.4 Pattern type 3 − tetra-substituted bis-salicylaldiminato M(II) complexes 86
5.3.5 Role of the N-alkyl side chains 91
5.3.6 Dynamics within the adlayers 94
5.3.7 Formation of double-layers 95
5.4 Conclusion 96
5.5 Experimental section 98
5.5.1 Ligand syntheses 98
5.5.2 Complex 101
5.6 References 103
6 Binuclear Metal Complexes − STM-Visualisation 107
6.1 Introduction 107
6.2 Syntheses of binuclear alkyl functionalised M(II) complexes 112
6.2.1 Bis-salicylaldiminato Cu(II) complex 112
6.2.2 Diazomethinephenolate Cu(II) complex 112
6.3 STM investigations 117
6.3.1 Binuclear bis-salicylaldiminato Cu(II) complex 117
6.3.2 Free alkoxy substituted diformylphenol ligand 117
6.3.3 Binuclear diazomethinephenolate Cu(II) complex 118
ii 6.4 Conclusion 119
6.5 Experimental section 120
6.5.1 Ligand syntheses 120
6.5.2 Complex 123
6.6 References 124
7 Functionalised Polyazamacrocycles 127
7.1 Introduction 127
7.2 Syntheses of flexible supramolecular Schiff-base macrocycles 129
7.2.1 Supramolecular dicarbaldehydes and diamines 130
7.2.2 Cyclisation reactions by dipodal [2+2] condensation 134
7.3 Schiff-base macrocycles bearing soluble side groups 137
7.3.1 Tert-butyl substituted diformylpyridine precursor 138
7.3.2 Alkoxy substituted diform139
7.4 Preparative GPC separation of [n+n] macrocycles 140
7.5 Alkoxy substituted totally π-conjugated macrocycles 143
7.5.1 Template syntheses of Robson macrocycles 144
7.5.2 Template synthesis of pyridyl m146
7.6 N-acylated aza-crown ethers 148
7.7 Conclusion 151
7.8 Experimental section 152
7.8.1 Diformyl and diamine reagents 152
7.8.2 Cyclisation reactions 161
7.8.3 Totally π-conjugated macrocycles 163
7.8.4 N-acylated aza-crown ethers 164
7.9 References 167
Appendix 171
Summary 181
Zusammenfassung 187




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