Chirality in Supramolecular Assemblies

Emeritus Professor F. Richard KeeneAdjunct 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 AdelaideRichard 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.

• List of Contributors xi Preface xiii1 Principles of Molecular Chirality 1Jean]Claude Chambron and F. Richard Keene1.1 General Introduction 11.2 Geometrical Chirality 21.3 Topological Chirality 251.4 Conclusion 39References 392 Homochirogenesis and the Emergence of Lifelike Structures 44Pedro Cintas2.1 Introduction and Scope 442.2 The Racemic State: Mirror Symmetry Breaking 452.3 Asymmetric Oligomerization 492.4 Biochirality in Active Sites 582.5 Conclusions 61Acknowledgements 61References 613 Aspects of Crystallization and Chirality 65Roger Bishop3.1 Introduction 653.2 Crystal Space Groups 653.3 Fundamentals of Crystallization for a Racemic Mixture 693.4 More Complex Crystallization Behavior 713.5 Multiple Crystal Forms 743.6 Conglomerates Revisited 85References 904 Complexity of Supramolecular Assemblies 94Jonathan A. Kitchen and Philip A. Gale4.1 Introduction 944.2 Generating Supramolecular Chirality through Assembly of Achiral Components 964.3 Enantioselective Supramolecular Assemblies 1214.4 Conclusions and Future Outlook 134References 1345 Chirality in the Host]Guest Behaviour of Supramolecular Systems 142Nicholas H. Evans and Paul D. Beer5.1 An Introduction to Chiral Recognition and its Importance 1425.2 Chiral Hosts for Chiral Guests 1435.3 Conclusions: Summary and Future Directions 155References 1566 Chiral Influences in Functional Molecular Materials 159David B. Amabilino6.1 Introduction 1596.2 Functional Molecular Materials in Different States 1616.3 Switching 1686.4 Conducting Materials 1716.5 Magnetic Materials 1736.6 Sensors 1776.7 Conclusions and Outlook 180Acknowledgements 181References 1817 Chirality in Network Solids 190David R. Turner7.1 Introduction 1907.2 Chirality in Inorganic Network Solids 1917.3 Synthesis of Chiral Coordination Polymers 1927.4 Applications of Chiral Coordination Polymers 2077.5 Summary and Outlook 209References 2108 Chiral Metallosupramolecular Polyhedra 218Jack K. Clegg and John C. McMurtrie8.1 Introduction 2188.2 Basic Design Principles 2198.3 Chiral Polyhedra from Achiral Components 2218.4 Stereochemical Communication 2318.5 Resolution of Racemic Metallo]Supramolecular Polyhedra 2368.6 Chiral Polyhedra from Chiral Molecular Components 2398.7 Conclusions and Outlook 250References 2519 Chirality at the Solution/Solid]State Interface 257Iris Destoop and Steven De Feyter9.1 Self]Assembly at the Solution / Solid]State Interface 2579.2 Chirality Expression at the Solution / Solid]State Interface 2589.3 Chiral Induction / Amplification at the Solution / Solid]State Interface 2669.4 Towards Applications 2789.5 Conclusions 282References 28210 Nanoscale Aspects of Chiral Nucleation and Propagation 285Edward G. Latter and Rasmita Raval10.1 Introduction 28510.2 Systems of Discussion 28810.3 Conclusions 303References 30411 Chirality in Organic Hosts 307Daniel Fankhauser and Christopher J. Easton11.1 Introduction 30711.2 Chiral Hosts in Analytical Applications 30711.3 Chiral Hosts in Asymmetric Reactions 31311.4 Conclusion 337Acknowledgements 338References 33812 Chirality Related to Biocatalysis and Enzymes in Organic Synthesis 343Declan P. Gavin and Anita R. Maguire12.1 Introduction 34312.2 Biocatalysis 34412.3 Biocatalytic Methodologies: Kinetic/Dynamic Kinetic Resolution and Asymmetric Transformations/Chemoselective Desymmetrizations 34812.4 Optimization of Biocatalyst Performance 35112.5 Protein Engineering 35212.6 Hydrolysis/Reverse Hydrolysis 35612.7 Redox Reactions 36612.8 C]C and Other C]X Bond Formation 38012.9 Future and Outlook 385References 385Index 407