Supramolecular Chemistry

A one-stop, comprehensive, and thoroughly updated resource for students, professors, and researchers alike

Thoroughly revised and updated, the Third Edition of Supramolecular Chemistry delivers a comprehensive and integrated approach to this rapidly evolving and quickly expanding field. Distinguished professors and authors Jonathan Steed and Jerry Atwood provide readers with a broad and exhaustive resource that assumes little in the way of prior knowledge of supramolecular chemistry.

Extensive new content on cutting edge research throughout the field including molecular machines and the mechanical bond, mechanochemistry, halogen bonding, and crystal nucleation accompanies full-color imagery and study problems designed to help students understand and apply the principles introduced within the book. Additional material is provided in the supplementary online resources, including solutions to the student exercises and PowerPoint slides of the figures in the book. Supramolecular Chemistry, Third Edition also includes:

• The latest research and developments reported over the last decade
• A unique "key references" system that highlights crucial reviews and primary literature
• A description of key experimental techniques included in accessible "boxes" for the non-expert
• Exercises and problems for students, complete with online solutions
• Full-color illustrations and imagery designed to facilitate learning and retention of the key concepts and state-of-the art of the field

Perfect for undergraduate and postgraduate students taking courses on supramolecular chemistry, the Third Edition of Supramolecular Chemistry also belongs on the bookshelves of all researchers in this, and any closely related, fields. Academics, in particular postdoctoral students and professors, will benefit significantly from this text.

Jonathan W. Steed is Professor of Inorganic Chemistry at Durham University. He obtained his Ph.D. at University College London. He is the recipient of the RSC Meldola Medal, Durham’s Vice Chancellor’s Award for Excellence in Postgraduate Teaching, the Bob Hay Lectureship, and the RSC Corday-Morgan Prize. 

Jerry L. Atwood is the Curator’s Distinguished Professor at the University of Missouri. He obtained his Ph.D. in 1968 at the University of Illinois. He is the co-founder of the journals Supramolecular Chemistry and the Journal of Inclusion Phenomena. He is the recipient of the Izatt-Christiansen Prize in Supramolecular Chemistry. 

About the Authors xvii

Preface to the Third Edition xix

Acknowledgements xxi

About the Front Cover xxiii

About the Companion Website xxiii

CHAPTER 1 Concepts 1

1.1 Definition and Development of Supramolecular Chemistry 1

1.2 Classification of Supermolecule Formation 4

1.3 Receptors, Coordination, and the Lock and Key Analogy 11

1.4 Binding Constants 14

1.5 Cooperativity, Multivalency, and the Chelate Effect 29

1.6 Preorganisation and Complementarity 36

1.7 Thermodynamic and Kinetic Selectivity, and Discrimination 38

1.8 Nature of Supramolecular Interactions 40

1.9 Solvation Effects 57

1.10 Supramolecular Concepts and Design 61

1.11 Practical Applications of Supramolecular Chemistry 73

CHAPTER 2 The Supramolecular Chemistry of Life 83

2.1 Biological Inspiration for Supramolecular Chemistry 83

2.2 Alkali Metal Cations in Biochemistry 84

2.3 Porphyrins and Tetrapyrrole Macrocycles 96

2.4 Supramolecular Features of Plant Photosynthesis 99

2.5 Uptake and Transport of Oxygen by Haemoglobin 106

2.6 Enzymes and Coenzymes 111

2.7 Signalling: Neurotransmitters, Hormones, and Pheromones 117

2.8 DNA and the Genetic Code 121

2.9 Biochemical Self-Assembly 134

2.10 Biomineralisation 137

2.11 Emergence of Life 141

CHAPTER 3 Cation-Binding Hosts 147

3.1 Introduction to Coordination Chemistry 147

3.2 Podands 153

3.3 The Crown and Lariat Ethers 158

3.4 The Cryptands 163

3.5 The Spherands 165

3.6 Nomenclature of Cation-Binding Macrocycles 167

3.7 Selectivity of Cation Complexation 169

3.8 Solution Behaviour and Applications of Crowns and Cryptands 184

3.9 Macrocycle Synthesis: The Template Effect and High Dilution 189

3.10 Soft Ligands for Soft Metal Ions 196

3.11 Proton Binding: The Simplest Cation 212

3.12 Complexation of Organic Cations 217

3.13 Alkalides and Electrides 231

3.14 The Calixarenes 234

3.15 Carbon Donor and π-acid Ligands 244

3.16 The Siderophores 250

CHAPTER 4 Anion Binding 265

4.1 Introduction 265

4.2 Biological Anion Receptors 268

4.3 Concepts in Anion Host Design 274

4.4 Cationic Receptors 283

4.5 Neutral Receptors 300

4.6 Boron Based Receptors and Lewis Acid Chelates 319

4.7 Metal-Containing Receptors 323

4.8 Anion-Binding Helices 333

4.9 Anion Transport 336

CHAPTER 5 Ion-Pair Receptors 351

5.1 Simultaneous Anion and Cation Binding 351

5.2 Labile Coordination Complexes and Cages as Anion Hosts 367

5.3 Receptors for Zwitterions 375

CHAPTER 6 Molecular Guests in Solution 381

6.1 Molecular Hosts and Molecular Guests 381

6.2 Intrinsic Curvature: Guest Binding by Cavitands 384

6.3 Cyclodextrins 401

6.4 Molecular Tweezers, Clips and Clefts 411

6.5 Cyclophane Hosts 415

6.6 Constructing a Solution Host from Clathrate-Forming Building Blocks: The Cryptophanes 440

6.7 Covalent Cages: Carcerands and Hemicarcerands 450

6.8 Coordination Cages 460

6.9 Halogen-Bonded Complexes 461

CHAPTER 7 Solid-State Inclusion Compounds 469

7.1 Nomenclature and Thermochemical Aspects 469

7.2 Porosity and Gas Sorption 473

7.3 Clathrate Hydrates 479

7.4 Urea and Thiourea Clathrates 486

7.5 Channel Clathrates 492

7.6 Polarity Formation 497

7.7 Hydroquinone, Phenol, Dianin's Compound, and the Hexahost Strategy 501

7.8 Macrocyclic Clathrates 504

7.9 Covalent Cages 522

7.10 Gas Sorption by Coordination Complex Hosts 527

CHAPTER 8 Crystal Engineering 537

8.1 Concepts 537

8.2 Crystal Nucleation and Growth 550

8.3 Understanding Crystal Structures 574

8.4 The Cambridge Structural Database 589

8.5 Polymorphism 592

8.6 Co-crystals 603

8.7 Solid State Transformations 617

8.8 Crystal Structure Prediction 624

8.9 Common and Exotic Supramolecular Synthons 629

8.10 Halogen Bonding 640

8.11 Bending and Jumping Crystals 642

CHAPTER 9 Network Solids 655

9.1 What are Network Solids? 655

9.2 Zeolites 662

9.3 Layered Solids and Intercalates 670

9.4 In the Beginning: Hoffman Inclusion Compounds and Werner Clathrates 676

9.5 Coordination Polymers 679

9.6 Porous Metal-Organic Frameworks 696

9.7 Covalent Organic Frameworks 716

CHAPTER 10 Self-Assembly 727

10.1 Introduction 727

10.2 Proteins and Foldamers: Single-Molecule Self-Assembly 733

10.3 Biochemical Self-Assembly 736

10.4 Self-Assembly in Synthetic Systems: Kinetic and Thermodynamic Considerations 739

10.5 Helicates and Helical Assemblies 755

10.6 Self-Assembling Coordination Compounds 768

10.7 Self-Assembly of Closed Complexes by Hydrogen Bonding 793

10.8 Templated Assembly of Porphyrin Arrays 805

10.9 Programmed Assembly with Biomolecules 807

CHAPTER 11 The Mechanical Bond 815

11.1 Scope and Importance of Mechanical Bonding and Mechanostereochemistry 815

11.2 Catenanes and Rotaxanes 816

11.3 Molecular Knots 846

11.4 Borromean Rings and Multiply Interlocked Catenanes 857

11.5 Interpenetrated Cages 860

11.6 An Unusual Thring 861

CHAPTER 12 Molecular Devices and Machines 867

12.1 Introduction 867

12.2 Supramolecular Photochemical Devices 870

12.3 Information and Signals: Semiochemistry and Sensing 890

12.4 Molecule-Based Electronics 909

12.5 Molecular Analogues of Mechanical Machines 923

CHAPTER 13 Biological Mimics and Supramolecular Catalysis 945

13.1 Introduction 945

13.2 Cyclodextrins as Enzyme Mimics 948

13.3 Corands as ATPASE Mimics 953

13.4 Cation-Binding Hosts as Transacylase Mimics 955

13.5 Metallobiosites 958

13.6 Enzyme Mimetic Materials 977

13.7 Ion Channel Mimics 978

13.8 Supramolecular Catalysis 985

CHAPTER 14 Interfaces and Liquid Assemblies 1003

14.1 Order in Liquids 1003

14.2 Surfactants and Interfacial Ordering 1005

14.3 Liquid Crystals 1018

14.4 Polyamorphous Liquids 1030

14.5 Ionic Liquids and Deep Eutectic Solvents 1032

14.6 Liquid Clathrates 1033

14.7 Porous Liquids 1036

CHAPTER 15 Supramolecular Materials 1043

15.1 Introduction 1043

15.2 Dendrimers 1044

15.3 Fractal Assemblies 1062

15.4 Covalent Polymers with Supramolecular Properties 1063

15.5 Self-Assembled Supramolecular Polymers 1068

15.6 Mechanically Interlocked Materials 1077

15.7 Supramolecular Gels 1084

15.8 Polymeric Liquid Crystals 1091

15.9 Biological Self-Assembled Materials 1093

CHAPTER 16 Dynamic Covalent Bonding and Complex Systems 1101

16.1 Chemistry Out of Equilibrium 1101

16.2 Dynamic Combinatorial Libraries 1102

16.3 Self-Replication 1106

16.4 Shapeshifting Molecules 1111

16.5 Dissipative Self-Assembly 1113

CHAPTER 17 Nanochemistry 1119

17.1 When Is Nano Really Nano? 1119

17.2 Nanotechnology: The 'Top-Down' and 'Bottom-Up' Approaches 1120

17.3 Templated and Biomimetic Morphosynthesis 1121

17.4 Nanoscale Photonics 1124

17.5 Microfabrication, Nanofabrication and Soft Lithography 1126

17.6 Assembly and Manipulation on the Nanoscale 1132

17.7 Nanoparticles 1144

17.8 Endohedral Fullerenes, Nanotubes and Graphene 1152

Index 1165

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