Supramolecular Assemblies Based on Electrostatic Interactions

This volume presents recent advances and current knowledge in the field of supramolecular assemblies based on electrostatic interactions. The flexibility and simplicity of constructing assemblies is explained via several examples, illustrations, figures, case studies, and historical perspectives. Moreover, as there is an increasing demand for the use of theoretical and computational models of the interaction strengths for assisting with the experimental studies, one chapter specifically focuses on the "modelling'' of supramolecular assemblies. Finally, various aspects of the recent advances of the field as well as potential future opportunities are discussed, with the goal being to stimulate critical discussions among the community and to encourage further discovery. This volume aims to inspire and guide fellow scientists and students working in this field and thus it provides a great tool for all researchers, graduates and professionals specializing on the topic. Preface 6 Contents 8 Contributors 10 Abbreviations 12 Nomenclature and Symbols 18 1 Supramolecular Ionic Networks: Design and Synthesis 20 1.1 Introduction 20 1.2 Different Types of Supramolecular Assemblies 23 1.2.1 Hydrogen Bond-Assisted Supramolecular Assemblies 23 1.2.2 Metal–Ligand Induced Supramolecular Assemblies 25 1.2.3 Supramolecular Assemblies Based on π–π Stacking Interaction 26 1.3 Supramolecular Assemblies Based on Electrostatic Interactions 27 1.3.1 Supramolecular Ionic Assemblies from Low Molecular Weight Molecules 28 1.3.2 Supramolecular Ionic Assemblies from Low Molecular Weight Molecules and Polymers 33 1.3.3 Supramolecular Ionic Assemblies from Polymers 36 1.4 Summary and Future Perspectives 39 References 40 2 Supramolecular Ionic Networks: Properties 47 2.1 Introduction 47 2.2 Different Properties of Supramolecular Ionic Networks 49 2.2.1 Morphology 49 2.2.2 Thermal Properties 51 2.2.3 Electrical Characteristics 53 2.2.4 Rheological Properties 56 2.2.5 Self-Healing Properties 64 2.3 Conclusions and Future Aspects 68 References 69 3 The Role of Electrostatic Interaction in the Self-assembly of Macroions 73 3.1 Introduction 74 3.2 Theoretical Challenges of Nanoscale Macroions—Between Simple Ions and Colloids 75 3.3 Self-assembly of Ideal Macroions Regulated by Electrostatic Interaction 76 3.3.1 The Discovery of Blackberry Structures 77 3.3.2 Driving Force for Blackberry Structure Formation 78 3.3.3 Macroion-Counterion Interaction 81 3.3.4 Features and Applications of Blackberry Structures 83 3.4 Self-assembly of Complex or Functionalized Macroions—Competition and Cooperation Among Different Attractive Forces 88 3.4.1 Electrostatic Interaction Versus Hydrophobic Interaction 88 3.4.2 Electrostatic Interaction Versus Hydrogen Bonding 90 3.4.3 Electrostatic Interaction Versus Cation-π Interaction 91 3.4.4 Electrostatic Interaction vs. Van Der Waals Forces 93 3.4.5 Multiple Interactions 94 3.4.6 Electrostatic Interaction vs. Geometrical Restrictions 95 3.5 Conclusion 99 References 99 4 Ionic Self-Assembly of Dendrimers 103 4.1 Introduction to Dendritic Polymers 103 4.2 Ionic Dendrimers 108 4.2.1 Dendrimers with Internal Charges 108 4.2.2 Surface-Charged Dendrimers 111 4.3 Ionic Self-assembly of Dendrimers in Bulk 111 4.3.1 Liquid Crystals 111 4.3.2 Liquid Crystal Dendrimers 114 4.3.3 Ionic Liquid Crystal Dendrimers 115 4.4 Ionic Self-assembly of Dendrimers in Solution 122 4.4.1 Self-assembly of Dendritic Amphiphiles 123 4.4.2 Unimolecular Micelles 128 4.5 Conclusions and Outlook 130 References 131 5 Nano-Objects by Spontaneous Electrostatic Self-Assembly in Aqueous Solution 137 5.1 Introduction 138 5.2 Polyelectrolytes as Building Bocks 139 5.3 Intermolecular Interactions for Self-Assembly 142 5.4 Polyelectrolyte-Polyelectrolyte Aggregates 143 5.5 Polyelectrolyte Assemblies with Block-Polyelectrolytes 144 5.6 Nano-objects by Electrostatic Self-assembly in Solution: The Principle 146 5.7 The Dendrimer-Dye Model System: Understanding the Structure Formation in Electrostatic Self-assembly 148 5.7.1 Structural Analysis 148 5.7.2 Particle Stabilization 152 5.7.3 Cooperative Binding of Dye Molecules 153 5.7.4 Assembly Thermodynamics: Understanding Particle Size 154 5.7.5 Assembly Thermodynamics: Understanding Particle Shape 158 5.8 Versaility of the Approach: Structural Variety Using Polyelectrolytes 160 5.9 Nano-Objects by Electrostatic Self-assembly: Beyond Polyelectrolytes 164 5.10 Switching Nanostructure and Properties 165 5.10.1 pH-Switchability 166 5.10.2 Light-Switchable Particle Size 168 5.10.3 Light-Triggerable Particle Shape 173 5.10.4 Switching Enzyme Activity 174 5.10.5 Photoacid Counterions as Switch in Electrostatic Self-assembly 176 5.10.6 Further Triggers 177 5.11 Conclusion 178 References 179 6 Electrostatic Layer-by-Layer Self-Assembly Method: A Physico-Chemical Perspective 186 6.1 Introduction 186 6.2 Assembly of LbL Films: Methodological Approaches 188 6.3 Polyelectrolyte Multilayer Growth 195 6.4 Charge Balance in Polyelectrolyte Multilayers 199 6.5 Adsorption Kinetics 203 6.6 Internal Structure 206 6.7 Conclusions 208 References 208 7 Supramolecular Assemblies Based on σ-hole Interactions 220 7.1 Introduction 220 7.2 Results and Discussion 222 7.2.1 Tetrel Bonding 222 7.2.2 Pnictogen Bonding 229 7.2.3 Chalcogen Bonding 235 7.2.4 Halogen Bonding 241 7.3 Concluding Remarks 246 References 247 8 Regium Bonds: A Bridge Between Coordination and Supramolecular Chemistry 259 8.1 Introduction 259 8.2 Results and Discussion 262 8.2.1 Theoretical Studies 262 8.2.2 Experimental Studies 270 8.3 Concluding Remarks 276 References 277 9 Aqueous Supramolecular Assemblies of Photocontrolled Molecular Amphiphiles 282 9.1 Introduction 282 9.2 Photoresponsive Charged Molecular Amphiphiles 284 9.3 Dynamic Functions of Photoresponsive Charged Molecular Amphiphiles at Air–Water Interfaces 286 9.4 Functional Supramolecular Self-assembly of Photoresponsive Charged Molecular Amphiphiles in Solution 297 9.4.1 Isotropic Self-assembly of Photoresponsive Charged Molecular Amphiphiles 297 9.4.2 Anisotropic Supramolecular Assembly of Photoresponsive Molecular Amphiphiles 308 9.5 Conclusion 313 References 315 10 Organic Salts as Tectons for Self-assembly Processes in Solution 324 10.1 Introduction 324 10.2 Imidazolium Salts 326 10.3 Ammonium Salts 344 10.4 Conclusions 351 References 352 11 Computational Modelling of Supramolecular Polymers 355 11.1 Introduction 355 11.2 Methodology 358 11.2.1 Density Functional Theory 358 11.2.2 Semi-empirical Methods 364 11.2.3 Molecular Mechanics and Molecular Dynamics Simulations 365 11.2.4 Coarse-Grained Molecular Dynamics 368 11.2.5 Solvent Models 369 11.2.6 Theoretical Aspects of Supramolecular Polymerization 371 11.3 Structural Models of Supramolecular Polymers and Polymerization Mechanisms 372 11.3.1 Supramolecular Polymerization at Quantum-Chemical Level 373 11.3.2 Supramolecular Polymerization by Classical Simulations 378 11.4 Transfer and Amplification of Chirality 381 11.5 Solvent Effects 385 11.6 Concluding Remarks 392 References 393 Index 399