Metallomacrocycles: From Structures to Applications / Edition 1

by Hai-Bo Yang

Overview

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.

Product Details

ISBN-13:	9781782628583
Publisher:	RSC
Publication date:	10/10/2018
Series:	ISSN , #27
Pages:	290
Product dimensions:	6.14(w) x 9.21(h) x (d)

About the Author

Hai-Bo Yang obtained his PhD degree at the Institute of Chemistry, Chinese Academy of Sciences (ICCAS) in Beijing in 2004. Then he joined Professor Peter J. Stang’s group at the University of Utah as a Postdoctoral Fellow. Since the end of 2008, he has started his independent research as a PI at East China Normal Universityin Shanghai. Prof. Yang’s research interests span the areas of organic, organometallic, and supramolecular chemistry.

Table of Contents

Chapter 1 Evolution of Metallomacrocycles From Macrocycles Wei Zheng Shu-Ting Jiang Bo Jiang Hai-Bo Yang 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 Bo Jiang Bo Ou Hai-Bo Yang 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 Xu-Qing Wang Wei-Jian Li Hai-Bo Yang 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 Li-Jun Chen Jun-Long Zhu Hai-Bo Yang 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 Macrocyeles Ying-Feng Han Guo-Xin Jin 106

References 117

Chapter 6 Supramolecular Transformations of Metallomacrocycles Wei Wang 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 M. R. Crawley T. R. Cook 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 Li-Jun Chen Jun-Long Zhu Hai-Bo Yang 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 Nem Singh Se Chan Rang Ki-Whan Chi 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 Metallacyele-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 Lin Xu Yi-Xiong Hu Partha Sarathi Mukherjee 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