Chirality in Supramolecular Assemblies Causes and Consequences

Supramolecular chemistry deals with the organisation of molecules into defined assemblies using non-covalent interactions, including weaker and reversible interactions such as hydrogen bonds, and metal-ligand interactions.  The aspect of stereochemistry within such chemical architectures, and in particular chirality, is of special interest as it impacts on considerations of molecular recognition, the development of functional materials, the vexed question of homochirality, nanoscale effects of interactions at interfaces, biocatalysis and enzymatic catalysis, and applications in organic synthesis.

Chirality in Supramolecular Assemblies addresses many of these aspects, presenting a broad overview of this important and rapidly developing interdisciplinary field. Topics covered include:

• Origins of molecular and topological chirality
• Homochirogenesis
• Chirality in crystallinity
• Host-guest behavior
• Chiral influences in functional materials
• Chirality in network solids and coordination solids
• Aspects of chirality at interfaces
• Chirality in organic assemblies
• Chirality related to biocatalysis and enzymes in organic synthesis.

This book is a valuable reference for researchers in the molecular sciences, materials science and biological science working with chiral supramolecular systems. It provides summaries and special insights by acknowledged international experts in the various fields.

Preface xiii

1 Principles of Molecular Chirality 1
Jean]Claude Chambron and F. Richard Keene

1.1 General Introduction 1

1.2 Geometrical Chirality 2

1.3 Topological Chirality 25

1.4 Conclusion 39

References 39

2 Homochirogenesis and the Emergence of Lifelike Structures 44
Pedro Cintas

2.1 Introduction and Scope 44

2.2 The Racemic State: Mirror Symmetry Breaking 45

2.3 Asymmetric Oligomerization 49

2.4 Biochirality in Active Sites 58

2.5 Conclusions 61

Acknowledgements 61

References 61

3 Aspects of Crystallization and Chirality 65
Roger Bishop

3.1 Introduction 65

3.2 Crystal Space Groups 65

3.3 Fundamentals of Crystallization for a Racemic Mixture 69

3.4 More Complex Crystallization Behavior 71

3.5 Multiple Crystal Forms 74

3.6 Conglomerates Revisited 85

References 90

4 Complexity of Supramolecular Assemblies 94
Jonathan A. Kitchen and Philip A. Gale

4.1 Introduction 94

4.2 Generating Supramolecular Chirality through Assembly of Achiral Components 96

4.3 Enantioselective Supramolecular Assemblies 121

4.4 Conclusions and Future Outlook 134

References 134

5 Chirality in the Host]Guest Behaviour of Supramolecular Systems 142
Nicholas H. Evans and Paul D. Beer

5.1 An Introduction to Chiral Recognition and its Importance 142

5.2 Chiral Hosts for Chiral Guests 143

5.3 Conclusions: Summary and Future Directions 155

References 156

6 Chiral Influences in Functional Molecular Materials 159
David B. Amabilino

6.1 Introduction 159

6.2 Functional Molecular Materials in Different States 161

6.3 Switching 168

6.4 Conducting Materials 171

6.5 Magnetic Materials 173

6.6 Sensors 177

6.7 Conclusions and Outlook 180

Acknowledgements 181

References 181

7 Chirality in Network Solids 190
David R. Turner

7.1 Introduction 190

7.2 Chirality in Inorganic Network Solids 191

7.3 Synthesis of Chiral Coordination Polymers 192

7.4 Applications of Chiral Coordination Polymers 207

7.5 Summary and Outlook 209

References 210

8 Chiral Metallosupramolecular Polyhedra 218
Jack K. Clegg and John C. McMurtrie

8.1 Introduction 218

8.2 Basic Design Principles 219

8.3 Chiral Polyhedra from Achiral Components 221

8.4 Stereochemical Communication 231

8.5 Resolution of Racemic Metallo]Supramolecular Polyhedra 236

8.6 Chiral Polyhedra from Chiral Molecular Components 239

8.7 Conclusions and Outlook 250

References 251

9 Chirality at the Solution/Solid]State Interface 257
Iris Destoop and Steven De Feyter

9.1 Self]Assembly at the Solution / Solid]State Interface 257

9.2 Chirality Expression at the Solution / Solid]State Interface 258

9.3 Chiral Induction / Amplification at the Solution / Solid]State Interface 266

9.4 Towards Applications 278

9.5 Conclusions 282

References 282

10 Nanoscale Aspects of Chiral Nucleation and Propagation 285
Edward G. Latter and Rasmita Raval

10.1 Introduction 285

10.2 Systems of Discussion 288

10.3 Conclusions 303

References 304

11 Chirality in Organic Hosts 307
Daniel Fankhauser and Christopher J. Easton

11.1 Introduction 307

11.2 Chiral Hosts in Analytical Applications 307

11.3 Chiral Hosts in Asymmetric Reactions 313

11.4 Conclusion 337

Acknowledgements 338

References 338

12 Chirality Related to Biocatalysis and Enzymes in Organic Synthesis 343
Declan P. Gavin and Anita R. Maguire

12.1 Introduction 343

12.2 Biocatalysis 344

12.3 Biocatalytic Methodologies: Kinetic/Dynamic Kinetic Resolution and Asymmetric Transformations/Chemoselective Desymmetrizations 348

12.4 Optimization of Biocatalyst Performance 351

12.5 Protein Engineering 352

12.6 Hydrolysis/Reverse Hydrolysis 356

12.7 Redox Reactions 366

12.8 C]C and Other C]X Bond Formation 380

12.9 Future and Outlook 385

References 385

Index 407

Emeritus Professor F. Richard Keene
Adjunct Professor of Chemistry, School of Pharmacy & Molecular Sciences, James Cook University, Australia and Department of Chemistry, University of Canterbury, New Zealand. Honorary Visiting Research Fellow, School of Chemistry & Physics, University of Adelaide
Richard Keene is an acknowledged international authority on stereochemistry in coordination chemistry - and significantly, in the control of stereochemistry within polymetallic supramolecular assemblies - and has over the last decade has published widely on (i) its effect on intramolecular electron and energy transfer in such assemblies, and (ii) its influence on sequence- and structure-selectivity in the interaction of such complexes with nucleic acids, and their cytotoxicity to cancer cells and bacteria. He has over 160 publications (h-index 44), as well 6 chapters in monographs and a patent.