Supramolecular Chemistry: From Concepts to Applications

Description

This book provides an accessible and timely introduction to the exciting interdisciplinary field of supramolecular chemistry. Starting with the principles that explain how molecules recognize each other and self-assemble non-covalently, an overview is given how these concepts can be used to create complex supramolecular architectures. One thus learns how to design functional molecular systems that serve as switches, motors, transporters, catalysts, chemosensors and much more. Introduces the concepts of molecular organization and self-assembly Explores the synthesis of interlocked molecules and supramolecular structures Addresses the applications of supramolecular systems (catalysis, molecular machines and devices) Cover Half Title Also of Interest Supramolecular Chemistry: From Concepts to Applications Copyright Dedication Preface Contents Questions discussed 1. Introduction and overview Bibliography 2. Analyzing complex formation 2.1 Thermodynamic and kinetic aspects 2.2 Analytical strategies and techniques 2.2.1 Strategies 2.2.2 NMR spectroscopy 2.2.3 UV–vis spectroscopy 2.2.4 Fluorescence spectroscopy 2.2.5 Potentiometry 2.2.6 Isothermal titration calorimetry Bibliography 3. Understanding molecular recognition 3.1 Modes of binding 3.1.1 General considerations 3.1.2 Ion–ion interactions 3.1.3 Ion–dipole interactions 3.1.4 Dipole–dipole interactions 3.1.5 Hydrogen bonding 3.1.6 Halogen bonding 3.1.7 Cation–π interactions 3.1.8 Anion–π interactions 3.1.9 Aromatic–aromatic interactions 3.1.10 Dispersion interactions 3.2 Binding energies 3.2.1 General considerations 3.2.2 Trend analyses 3.2.3 Double-mutant cycles 3.2.4 Molecular balances 3.3 Solvent effects 3.4 Predicting binding strength in solution 3.5 Guidelines for receptor design 3.5.1 Complementarity, preorganization, and induced fit 3.5.2 Chelate effect and macrocyclic effect 3.5.3 Multivalency and cooperativity 3.5.4 Allosterism and cooperativity Bibliography 4. Hosting ions and molecules 4.1 Receptors 4.1.1 Crown ethers 4.1.2 Cryptands 4.1.3 Spherands 4.1.4 Cyclodextrins 4.1.5 Cyclophanes 4.1.6 Cyclotriveratrylenes 4.1.7 Calixarenes 4.1.8 Calixpyrroles 4.1.9 Resorcinarenes 4.1.10 Pillararenes 4.1.11 Cucurbiturils 4.1.12 Clefts and tweezers 4.1.13 Foldamers 4.2 Substrates 4.2.1 Inorganic and organic cations 4.2.2 Inorganic and organic anions 4.2.3 Zwitterions and ion pairs 4.2.4 Neutral organic molecules Bibliography 5. Assembling molecules 5.1 Self-assembly and template effects 5.2 Self-assembly mediated by the hydrophobic effect 5.3 Self-assembly mediated by hydrogen bonds 5.3.1 Introduction 5.3.2 Rosettes 5.3.3 Capsules 5.3.4 Tubes 5.4 Self-assembly mediated by halogen bonds 5.4.1 Introduction 5.4.2 Helices 5.4.3 Capsules 5.5 Self-assembly mediated by coordination bonds 5.5.1 Introduction 5.5.2 Helices 5.5.3 Grids 5.5.4 Rings 5.5.5 Cages 5.6 Self-assembly mediated by covalent bonds 5.6.1 Introduction 5.6.2 Rings 5.6.3 Cages 5.7 Dynamic combinatorial chemistry 5.7.1 Introduction 5.7.2 Casting 5.7.3 Molding 5.7.4 Self-assembly 5.8 Systems chemistry Bibliography 6. Threading molecules 6.1 Molecular topology 6.2 Synthetic strategies 6.2.1 Molecular strategies 6.2.2 Supramolecular strategies 6.3 Syntheses using metal coordination 6.3.1 Catenanes 6.3.2 Knots 6.3.3 Rotaxanes 6.4 Syntheses using charge-transfer interactions 6.4.1 Catenanes 6.4.2 Rotaxanes 6.5 Syntheses using hydrogen bonds 6.5.1 Catenanes 6.5.2 Knots 6.5.3 Rotaxanes 6.6 Syntheses using halogen bonds 6.6.1 Rotaxanes 6.7 Syntheses using the hydrophobic effect 6.7.1 Knots 6.7.2 Rotaxanes Bibliography 7. Controlling molecular motion 7.1 Introduction 7.2 Rotaxane-derived machines 7.3 Catenane-derived machines 7.4 Machines without mechanical bonds Bibliography 8. Mediating molecular transformations 8.1 Introduction 8.2 Stoichiometric transformations 8.2.1 Transformation by functional group participation 8.2.2 Transformation by confinement 8.3 Catalytic transformations 8.3.1 Transformation by functional group participation 8.3.2 Transformation by confinement 8.4 Self-replication Bibliography 9. Transporting molecules 9.1 Introduction 9.2 Cation transport 9.2.1 Channels 9.2.2 Carriers 9.3 Anion transport 9.3.1 Channels 9.3.2 Carriers 9.4 Water transport Bibliography 10. Detecting molecules 10.1 Introduction 10.2 Single analyte sensing 10.2.1 Direct optical sensing 10.2.2 Indirect optical sensing 10.2.3 Direct electrochemical sensing 10.3 Multiple analyte sensing Bibliography 11. Applying supramolecular systems 11.1 Introduction 11.2 Applications in medicine 11.2.1 Drugs 11.2.2 Drug formulations 11.2.3 Imaging 11.3 Applications in separation processes 11.3.1 Chromatography 11.3.2 Extraction 11.3.3 Precipitation 11.4 Applications in materials chemistry 11.4.1 Self-assembled polymers 11.4.2 Polymer networks 11.4.3 Self-assembled gels 11.5 Applications in catalysis 11.6 Applications in molecular electronics 11.7 Applications in consumer products 11.7.1 Textiles 11.7.2 Food 11.7.3 Household Bibliography 12. Appendices 12.1 Concentrations in a 1:2 binding equilibrium 12.2 Concentrations in an indicator displacement assay Bibliography Index