Explore the cutting-edge in 2D chemistry on surfaces and its applications
In Supramolecular Chemistry on Surfaces: 2D Networks and 2D Structures, expert chemist Neil R. Champness delivers a comprehensive overview of the rapidly developing field of two-dimensional supramolecular chemistry on surfaces. The book offers explorations of the state-of-the-art in the discipline and demonstrates the potential of the latest advances and the challenges faced by researchers in different areas.
The editor includes contributions from leading researchers that address new spectroscopic methods which allow for investigations at a sub-molecular level, opening up new areas of understanding in the field. Included resources also discuss important supramolecular strategies, like hydrogen-bonding, van der Waals interactions, metal-ligand coordination, multicomponent assembly, and more. The book also provides: - A thorough introduction to two-dimensional supramolecular chemistry on surfaces - Comprehensive explorations of the characterization and interpretation of on-surface chemical reactions studied by ultra-high resolution scanning probe microscopy - Practical discussions of complexity in two-dimensional multicomponent assembly, including explorations of coordination bonds and quasicrystalline structures - In-depth examinations of covalently bonded organic structures via on-surface synthesis
Perfect for polymer chemists, spectroscopists, and materials scientists, Supramolecular Chemistry on Surfaces: 2D Networks and 2D Structures will also earn a place in the libraries of physical and surface chemists, as well as surface physicists.
Table of Contents
Preface ix
1 Two-Dimensional Supramolecular Chemistry on Surfaces 1
Neil R. Champness
References 6
2 Characterisation and Interpretation of On-Surface Chemical Reactions Studied by Ultra-High-Resolution Scanning Probe Microscopy 9
Adam Sweetman, Neil R. Champness, and Alex Saywell
2.1 Introduction 9
2.2 SPM Under UHV Conditions 10
2.2.1 On-Surface Reactions 11
2.2.2 Characterisation of Molecule-Substrate Systems via STM 12
2.2.3 ncAFM 15
2.3 Practical Steps in Accomplishing Sub-Molecular Imaging 16
2.3.1 Sample Preparation 16
2.3.1.1 Deposition of Organic Molecules at Low Temperature 17
2.3.1.2 CO Deposition 17
2.3.1.3 Decoupling Layers 18
2.3.2 Construction of the qPlus Sensor 18
2.3.3 Tip Preparation 19
2.3.3.1 Tip Functionalisation 19
2.3.4 Practical Considerations for Imaging 21
2.3.4.1 Drift and Creep 21
2.3.4.2 Amplitude Calibration 22
2.3.4.3 Apparent Dissipation and Mechanical Coupling of the Sensor 22
2.3.4.4 Crosstalk 22
2.3.4.5 Force Inversion 23
2.4 Interpretation of Sub-Molecular Contrast at the Single Bond Level 23
2.4.1 Forces in the Tip-Sample Junction 24
2.4.1.1 Non-site Specific Interactions - The ‘Background’ 24
2.4.1.2 Local Dispersion Interactions - The ‘Halo’ 24
2.4.1.3 Pauli Repulsion - The ‘Carbon Backbone’ 24
2.4.1.4 Chemical Bonding 25
2.4.1.5 Local Electrostatic Interactions 25
2.4.2 Response of the Probe Particle - Distortions in Imaging 25
2.4.2.1 Flexibility of Adsorbed CO 26
2.4.2.2 Electrostatics 28
2.4.2.3 Chemical Sensitivity 29
2.5 Characterising On-Surface Reactions with ncAFM 29
2.5.1 Practical Considerations for Characterising On-Surface Reactions 31
2.5.2 Synthesis and Characterisation of Graphene Based Nanostructures 32
2.5.3 Studying the Evolution of On-Surface Reaction 34
2.6 Conclusions 38
Acknowledgements 39
References 39
3 Complexity in Two-Dimensional Multicomponent Assembly 43
Kunal S. Mali, Joan Teyssandier, Nerea Bilbao, and Steven De Feyter
3.1 Introduction 43
3.2 Two-Component Self-Assembled Systems 45
3.2.1 Two-Component Systems: Host-Guest Architectures 46
3.2.1.1 Host Networks from Intrinsically Porous Building Blocks 46
3.2.1.2 Host Networks from Self-Assembly of Building Blocks 49
3.2.1.3 Two-Component Systems: Host-Guest Architectures Based on Surface-Confined Two-Dimensional Covalent Organic Frameworks (2D-sCOFs) 57
3.2.2 Two-Component Systems: Non-Host-Guest Architectures 59
3.3 Three-Component Systems 62
3.3.1 Three-Component Systems: Two-Component Host Network + Guest 62
3.3.2 Three-Component Systems: One-Component Host Network + Two Different Guests 65
3.3.3 Three-Component Systems: Non-host-Guest Systems 69
3.4 Four-Component Systems 71
3.4.1 Four-Component Systems: Host-Guest Architectures 72
3.4.2 Four-Component Systems: Non-host-Guest Architectures 75
3.5 Summary and Perspectives 76
References 76
4 Complexity in Two-Dimensional Assembly: Using Coordination Bonds 81
Nian Lin and Jing Liu
4.1 Introduction 81
4.2 Asymmetric Linkers 82
4.3 Multiple Types of Linkers 86
4.4 Multiple-Level (Hierarchical) Interaction 88
4.5 Multiple Binding Modes 90
4.6 Summary and Outlook 97
References 97
5 Complexity in Two-Dimensional Assembly: Quasicrystalline Structures 103
S. Alex Kandel
History 103
Random Tilings 104
Quasicrystalline Tilings 108
References 114
6 Using Self-Assembly to Control On-Surface Reactions 117
Zhantao Peng, Lingbo Xing, and Kai Wu
6.1 Introduction 117
6.2 Mediating On-Surface Reaction Selectivity 119
6.3 Mediating On-Surface Reaction Pathway 124
6.4 Mediating On-Surface Reaction Site 125
6.5 Brief Summary and Perspective 130
Acknowledgement 131
References 131
7 Covalently Bonded Organic Structures via On-Surface Synthesis 135
Can Wang, Haiming Zhang, and Lifeng Chi
7.1 Introduction 135
7.2 Dehalogenation 136
7.2.1 Ullmann Coupling 136
7.2.2 Sonogashira Coupling 141
7.2.3 Heck Reaction 141
7.3 Dehydrogenation 143
7.3.1 (SP 3 -C) Alkane Polymerisation 143
7.3.2 (SP 2 -C) Aryl and Alkene Cyclodehydrogenation 145
7.3.2.1 Aryl-Aryl Dehydrogenation Coupling 145
7.3.2.2 Bottom-Up Fabrication of Graphene Nanoribbons (GNRs) 148
7.3.2.3 Homo-Coupling of Terminal Alkene 150
7.3.3 (SP 1 -C) Alkyne - Glaser Coupling 151
7.3.4 Hierarchical Dehydrogenation of X - H Bonds (X = N and C) 152
7.4 Dehydration Reaction 153
7.4.1 Schiff-Base Reaction 153
7.4.2 Imidisation Condensation Reaction 156
7.4.3 Boronic Acid Condensation 156
7.4.4 Decarboxylative Polymerisation 157
7.4.5 Dimerisation and Cyclotrimerisation of Acetyls 159
7.5 Other Reactions 159
7.5.1 Click Reaction 159
7.5.1.1 Azide-Alkyne Cycloaddition 159
7.5.1.2 Diels-Alder Reaction 160
7.5.2 Bergman-Like Reaction 161
7.5.3 N-Heterocyclic Carbenes Formation and Dimerisation 162
7.5.4 σ-Bond Metathesis 163
7.5.5 Diacetylene Polymerisation 164
7.6 Conclusion and Perspectives 165
References 166
8 Hybrid Organic-2D TMD Heterointerfaces: Towards Devices Using 2D Materials 171
Yu L. Huang and Andrew T. S. Wee
8.1 Introduction 171
8.2 Atomic Structures 172
8.2.1 Pristine 2D TMDs 172
8.2.2 Organic/2D TMD Interfaces 174
8.3 Surface Functionalisation of 2D TMDs by Organics 177
8.3.1 Defect Engineering 177
8.3.2 Phase Engineering 179
8.4 Fundamental Electronic Properties 180
8.4.1 Energy Level Alignment 181
8.4.2 Interfacial Charge Transfer 184
8.4.3 Screening Effect 190
8.5 Applications in Devices: Organic-2D TMD p-n Heterojunctions 192
8.6 Conclusion 193
Acknowledgements 194
References 194
9 Surface Self-Assembly of Hydrogen-Bonded Frameworks 199
Nicholas Pearce and Neil R. Champness
9.1 Introduction 199
9.2 Carboxylic Acid Supramolecular Synthons 200
9.3 Imide-Melamine Supramolecular Synthons 205
9.4 From Hydrogen-bonding Synthons to Covalently-organic Frameworks 211
9.5 Heteromolecular Hydrogen-bonding Synthons 213
9.6 Conclusions 215
References 215
Index 219
