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Abstract
The metal–ligand coordination of metallomacrocycles allows for the production of both discrete and infinite metallosupramolecular structures with high-degrees of complexity. In recent years, coordination-driven self-assembly has emerged as a powerful noncovalent synthetic strategy to build discrete supramolecular architectures with diverse coordination moieties such as a well-defined shape, size, and geometry. The dynamic features of the metal–ligand bonds result in structures with intriguing properties allowing for a diverse range of applications in host–guest chemistry, sensing, drug delivery and catalysis.
This book provides a comprehensive summary of current research in metallomacrocycles. Starting with an introduction to metallomacrocycles constructed via coordination-driven self-assembly, the book then goes on to explore design principles and self-organization. Subsequent chapters then discuss examples of complex and functional metallosupramolecular systems based on metallomacrocycles such as chiral systems and mechanically interlocked architectures. Finally, the book discusses the applications of metallomacrocycles.
An essential resource for students and researchers looking to design and construct new metallosupramolecular systems and extend their applications in biological and materials science.
Table of Contents
| Section Title | Page | Action | Price |
|---|---|---|---|
| Cover | Cover | ||
| Metallomacrocycles: From Structures to Applications | i | ||
| Preface | v | ||
| Contents | ix | ||
| Chapter 1 - Evolution of Metallomacrocycles From Macrocycles | 1 | ||
| 1.1 Macrocycles | 1 | ||
| 1.2 Coordination-driven Self-assembly | 3 | ||
| 1.3 Two-dimensional Assembly of Metallomacrocycles | 6 | ||
| 1.4 Characterization of Metallomacrocycles | 11 | ||
| 1.4.1 Mass Spectrometry | 11 | ||
| 1.4.2 X-ray Measurement | 13 | ||
| 1.5 The Essential Characteristic of Metallomacrocycles | 14 | ||
| 1.5.1 Charged Systems | 14 | ||
| 1.5.2 The Dynamic Characteristic of Metallomacrocycles | 15 | ||
| 1.6 Conclusion and Outlook | 16 | ||
| Acknowledgements | 17 | ||
| References | 18 | ||
| Chapter 2 - Design Principles of Self-assembled Metallomacrocycles | 20 | ||
| 2.1 Introduction | 20 | ||
| 2.2 The Directional-bonding Approach | 21 | ||
| 2.2.1 Molecular Rhomboids | 23 | ||
| 2.2.2 Molecular Triangles | 25 | ||
| 2.2.3 Molecular Squares | 30 | ||
| 2.2.4 Molecular Hexagons | 35 | ||
| 2.3 The Symmetry-interaction Approach | 37 | ||
| 2.4 The Weak-link Approach | 39 | ||
| 2.5 Conclusion | 42 | ||
| Acknowledgements | 43 | ||
| References | 43 | ||
| Chapter 3 - Self-organization in Coordination-driven Self-assembled Metallomacrocyles | 47 | ||
| 3.1 Introduction | 47 | ||
| 3.2 Two-component Self-organization Systems | 48 | ||
| 3.3 Three-component Self-organization Systems | 54 | ||
| 3.4 Multicomponent Self-organization Systems | 65 | ||
| 3.5 Conclusion | 74 | ||
| Acknowledgements | 75 | ||
| References | 75 | ||
| Chapter 4 - Self-assembled Chiral Metallomacrocycles | 77 | ||
| 4.1 Introduction | 77 | ||
| 4.2 Synthetic Strategies for Self-assembled Chiral Metallomacrocycles | 78 | ||
| 4.2.1 Introduction of Chiral Bridging Ligands | 78 | ||
| 4.2.2 Use of Chiral Metal Auxiliaries that Possess Chiral Capping Groups | 89 | ||
| 4.2.3 Use of Inherently Chiral Metal Centres Having Specific Coordination Geometries | 92 | ||
| 4.3 Applications of Self-assembled Chiral Metallomacrocycles | 95 | ||
| 4.3.1 Chiral Sensing | 96 | ||
| 4.3.2 Asymmetric Catalysis | 98 | ||
| 4.4 Conclusions | 101 | ||
| Acknowledgements | 102 | ||
| References | 102 | ||
| Chapter 5 - Half-sandwich Iridium- and Rhodium-based Organometallic Macrocycles | 106 | ||
| References | 117 | ||
| Chapter 6 - Supramolecular Transformations of Metallomacrocycles | 120 | ||
| 6.1 Introduction | 120 | ||
| 6.2 Supramolecular Transformations Between Metallomacrocycles and One-dimensional Metallosupramolecular Polymers | 121 | ||
| 6.3 Supramolecular Transformations Between Metallomacrocycles and Another Two-dimensional Metallomacrocycles | 124 | ||
| 6.4 Supramolecular Transformations Between Metallomacrocycles and 3D Metallocages | 142 | ||
| 6.5 Conclusion | 149 | ||
| Acknowledgements | 149 | ||
| References | 149 | ||
| Chapter 7 - Coordination-driven Self-assembly of Functionalized Self-assembled Metallomacrocycles | 152 | ||
| 7.1 Introduction | 152 | ||
| 7.1.1 Sites of Functionalization | 155 | ||
| 7.1.2 Pre- versus Post-self-assembly | 157 | ||
| 7.2 Photophysical Properties | 159 | ||
| 7.2.1 Introduction | 159 | ||
| 7.2.2 Covalently Append Dyes | 159 | ||
| 7.2.3 Sensor Applications | 162 | ||
| 7.2.4 Effects of Functional Groups on Photophysical Properties | 164 | ||
| 7.2.5 BODIPY-functionalized Metallomacrocycles | 164 | ||
| 7.3 Electrochemically Active Materials | 166 | ||
| 7.3.1 Introduction | 166 | ||
| 7.3.2 Functionalization with dppf Ligands | 166 | ||
| 7.3.3 Covalently Tethered Ferrocene | 167 | ||
| 7.3.4 Fc/Dendrimer Hybrid Materials | 171 | ||
| 7.4 Dendrimer and Polymer Interfaces | 173 | ||
| 7.4.1 Introduction | 173 | ||
| 7.4.2 Functionalized Building Block Approach to Dendrimer-functionalized Metallacycles | 174 | ||
| 7.4.3 Metallacycles with Polymeric Functionalities | 177 | ||
| 7.5 Host–Guest Chemistry | 180 | ||
| 7.5.1 Introduction | 180 | ||
| 7.5.2 Cation Functionalized for Host–Guest Chemistry | 181 | ||
| 7.5.3 Pendant Groups for Host–Guest Chemistry | 181 | ||
| 7.5.4 Host–Guest Sensors | 184 | ||
| 7.6 Catalytically Active Species | 184 | ||
| 7.6.1 Introduction | 184 | ||
| 7.6.2 Synthetic Organic Catalysis | 185 | ||
| 7.6.3 Small-molecule Activation | 189 | ||
| 7.7 Conclusion | 190 | ||
| References | 191 | ||
| Chapter 8 - Higher-order Supramolecular Systems Derived From Self-assembled Metallomacrocycles | 195 | ||
| 8.1 Introduction | 195 | ||
| 8.2 Hydrophobic/Hydrophilic Effects as Secondary Driving Force | 197 | ||
| 8.3 Hydrogen Bonding as Secondary Driving Force | 202 | ||
| 8.4 π–π Stacking and CH–π Interaction Imposed by Dendrimers as Secondary Driving Force | 206 | ||
| 8.5 Host–Guest Interaction as Secondary Driving Force | 210 | ||
| 8.6 Electrostatic Interactions as Secondary Driving Force | 214 | ||
| 8.7 Multiple Secondary Driving Forces | 216 | ||
| 8.8 Conclusions | 220 | ||
| Acknowledgements | 222 | ||
| References | 222 | ||
| Chapter 9 - Applications of Self-assembled Metallomacrocycles I: Biological Applications | 226 | ||
| 9.1 Introduction | 226 | ||
| 9.2 Anticancer Activity of Self-assembled Metallomacrocycles | 227 | ||
| 9.2.1 Anticancer Activity of Ru-based Metallomacrocycles | 228 | ||
| 9.2.2 Anticancer Activities of Metallomacrocycles of Other Transition Metals | 235 | ||
| 9.3 Studies Conducted on Metallomacrocycle Binding with DNA and Proteins | 237 | ||
| 9.3.1 Metallomacrocycle–DNA Binding | 237 | ||
| 9.3.2 Metallacycle–Protein Binding | 240 | ||
| 9.4 Drug Delivery Using Metallomacrocycles | 241 | ||
| 9.5 Biological Evaluation Experiments | 243 | ||
| 9.5.1 Human Cell Culture | 243 | ||
| 9.5.2 In vitro Cytotoxicity Assay | 244 | ||
| 9.5.3 In vitro Drug Release Kinetics | 244 | ||
| 9.5.4 In vitro Fluorescence Microscopy of PDTC/DOX-loaded Nanoparticles | 244 | ||
| 9.5.5 Clonogenic Survival Assay | 244 | ||
| 9.5.6 Detection of Apoptotic Cells | 245 | ||
| 9.6 Conclusions | 245 | ||
| Acknowledgements | 245 | ||
| References | 245 | ||
| Chapter 10 - Applications of Self-assembled Metallomacrocycles II: Catalysis and Sensing | 251 | ||
| 10.1 Introduction | 251 | ||
| 10.2 Self-assembled Metallomacrocycles for Catalysis Applications | 252 | ||
| 10.3 Self-assembled Metallomacrocycles for Sensing | 260 | ||
| 10.4 Conclusions | 280 | ||
| Acknowledgement | 280 | ||
| References | 281 | ||
| Subject Index | 283 |