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Davis F., Higson S. Macrocycles (Wiley, 2011)(ISBN 047071462X)(O Macrocycles Macrocycles: onstruction,C Chemistr y and Nanotechnology Applications, First Edition. Frank D andavis Seamus´ Higs on. © 2011 J ohn Wiley& Sons , Ltd. ublisP hed 2011 by J ohn Wiley & Sons , Ltd. ISBN: 978-0-470-71462-1 Macrocycles Construction, Chemistry and Nanotechnology Applications FRANK DAVIS Cranfield Health, Cranfield University, Bedfordshire, UK SEAMUS´ HIGSON Cranfield Health, Cranfield University, Bedfordshire, UK A John Wiley and Sons, Ltd., Publication This edition first published 2011 c 2011 John Wiley & Sons, Ltd Registered office John Wiley & Sons Ltd, The Atrium, Southern Gate, Chichester, West Sussex, PO19 8SQ, United Kingdom For details of our global editorial offices, for customer services and for information about how to apply for permission to reuse the copyright material in this book please see our website at www.wiley.com. The right of the author to be identified as the author of this work has been asserted in accordance with the Copyright, Designs and Patents Act 1988. All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording or otherwise, except as permitted by the UK Copyright, Designs and Patents Act 1988, without the prior permission of the publisher. Wiley also publishes its books in a variety of electronic formats. Some content that appears in print may not be available in electronic books. Designations used by companies to distinguish their products are often claimed as trademarks. All brand names and product names used in this book are trade names, service marks, trademarks or registered trademarks of their respective owners. The publisher is not associated with any product or vendor mentioned in this book. This publication is designed to provide accurate and authoritative information in regard to the subject matter covered. It is sold on the understanding that the publisher is not engaged in rendering professional services. If professional advice or other expert assistance is required, the services of a competent professional should be sought. The publisher and the author make no representations or warranties with respect to the accuracy or completeness of the contents of this work and specifically disclaim all warranties, including without limitation any implied warranties of fitness for a particular purpose. This work is sold with the understanding that the publisher is not engaged in rendering professional services. The advice and strategies contained herein may not be suitable for every situation. In view of ongoing research, equipment modifications, changes in governmental regulations, and the constant flow of information relating to the use of experimental reagents, equipment, and devices, the reader is urged to review and evaluate the information provided in the package insert or instructions for each chemical, piece of equipment, reagent, or device for, among other things, any changes in the instructions or indication of usage and for added warnings and precautions. The fact that an organization or Website is referred to in this work as a citation and/or a potential source of further information does not mean that the author or the publisher endorses the information the organization or Website may provide or recommendations it may make. Further, readers should be aware that Internet Websites listed in this work may have changed or disappeared between when this work was written and when it is read. No warranty may be created or extended by any promotional statements for this work. Neither the publisher nor the author shall be liable for any damages arising herefrom. Library of Congress Cataloging-in-Publication Data Higson, Seamus.´ Macrocycles : construction, chemistry, and nanotechnology applications / Frank Davis, Seamus´ Higson. p. cm. Includes bibliographical references and index. ISBN 978-0-470-71462-1 (hardback) – ISBN 978-0-470-71463-8 (paper) – ISBN 978-1-119-98993-6 (ebook) 1. Macrocyclic compounds. I. Davis, Frank, 1966- II. Title. QD400.H54 2011 547.5–dc22 2010045660 A catalogue record for this book is available from the British Library. Print ISBN Cloth: 9780470714621 Print ISBN Paper: 9780470714638 ePDF ISBN: 9781119989936 oBook ISBN: 9780470980200 ePub ISBN: 9781119990291 Typeset in 10/12pt Times by Laserwords Private Limited, Chennai, India PrintedinMalaysiabyHoPrinting(M)SdnBhd Contents Preface xi 1 Introduction 1 1.1 Simple Ring Compounds 1 1.2 Three-Dimensional Aliphatic Carbon Structures 3 1.3 Annulenes 5 1.4 Multi-Ring Aromatic Structures 9 1.5 Porpyrins and Phthalocanines 10 1.6 Conclusions 13 References 14 2 Cyclophanes 16 2.1 Introduction 16 2.2 Cyclophanes with One Aromatic System and Aliphatic Chain 16 2.2.1 Properties of the cyclophanes 17 2.2.2 Chemistry of the cyclophanes 18 2.2.3 Synthesis of the cyclophanes 19 2.3 Cyclophanes with More than One Aromatic Ring 20 2.4 Napthalenophanes and Other Aromatic Systems 25 2.5 Cyclophanes Containing Heteroaromatic Systems 28 2.6 Ferrocenophanes 28 2.7 Conclusions 30 Bibliography 30 References 30 3 Crown Ethers, Cryptands and Other Compounds 34 3.1 Introduction 34 3.2 Crown Ethers 35 3.3 Simple Complexes with Crown Ethers 37 3.4 Azacrowns, Cyclens and Cyclams 42 3.5 Crowns Containing Other Heteroatoms 50 3.6 Lariat and Bibracchial Crown Ethers 50 3.7 Cryptands 54 3.8 Spherands 56 3.9 Combined and Multiple Systems 60 vi Contents 3.10 Applications of Crown Ethers and Related Compounds 67 3.11 Conclusions 70 Bibliography 70 References 70 4 Calixarenes 77 4.1 Introduction 77 4.2 History 77 4.3 Structures of Calixarenes 80 4.4 Chemical Modification of Calixarenes 82 4.4.1 Modification of the hydroxyls 82 4.4.2 Replacement of the hydroxyls 86 4.4.3 Reaction of the rings 88 4.4.4 Reactions of the bridging groups 89 4.4.5 Modification of the upper rim 90 4.5 Complexes with Calixarenes 95 4.6 Bis and Multicalixarenes 98 4.7 Oxacalixarenes, Azacalixarenes and Thiacalixarenes 104 4.8 Resorcinarenes: Synthesis and Structure 107 4.9 Cavitands and Carcerands 113 4.10 Conclusions 116 Bibliography 116 References 117 5 Heterocalixarenes and Calixnaphthalenes 126 5.1 Introduction 126 5.2 Calixnaphthalenes 126 5.3 Tropolone-Based Macrocycles 133 5.4 Calixfurans 134 5.5 Calixpyrroles 138 5.5.1 Introduction 138 5.5.2 Chemical modification of the calixpyrroles 146 5.5.3 Confused calixpyrroles 152 5.5.4 Substituted calixpyrroles 153 5.5.5 Strapped calixpyrroles 158 5.5.6 Modification of the pyrrole units 160 5.5.7 Sensing and other applications of calix[4]pyrroles 161 5.5.8 Calixpyrroles including nonpyrrole units 163 5.6 Calixindoles, Calixpyridines and Calixthiophenes 172 5.7 Conclusions 180 Bibliography 183 References 183 6 Cyclodextrins 190 6.1 Introduction 190 Contents vii 6.2 Complex Formation by Cyclodextrins 195 6.3 Cyclodextrins of Other Sizes 207 6.4 Modification Reactions of Cyclodextrins 208 6.4.1 Modification of the 6-hydroxyls 209 6.4.2 Modification of the 2- or 3-positions 211 6.5 Selectivity of Cyclodextrins 217 6.6 Multiple Cyclodextrin Systems 219 6.6.1 Bis and multi-cyclodextrins 219 6.7 Polymeric Cyclodextrins 229 6.7.1 Covalently linked cyclodextrin polymers 229 6.7.2 Noncovalently linked cyclodextrin polymers 231 6.8 Cyclodextrins Combined with Other Macrocyclic Systems 231 6.9 Therapeutic Uses of Cyclodextrins 235 6.10 Other Uses of Cyclodextrins 238 6.11 Conclusions 243 Bibliography 244 References 244 7 Cyclotriveratylenes and Cryptophanes 255 7.1 Introduction 255 7.2 Synthesis of Cyclotriveratrylenes 255 7.3 Modification of Cyclotriveratrylenes 263 7.4 Synthesis of Optically Active Cyclotriveratrylenes 268 7.5 Modification of the Bridging Groups 269 7.6 Modification of the Aromatic Rings with Organometallic Groups 273 7.7 Selective Binding Applications of Cyclotriveratrylenes 276 7.8 Analogues of CTV 287 7.9 Synthesis and Structure of Cryptophanes 289 7.10 Modification of Cryptophanes 299 7.11 Complexes with Cryptophanes 303 7.12 Cryptophane–Xenon Complexes 308 7.13 Other Uses of Cryptophanes 312 7.14 Hemicryptophanes 313 7.15 Conclusions 315 Bibliography 316 References 316 8 Cucurbiturils 325 8.1 Introduction 325 8.2 Complexation Behaviour of Simple Cucurbiturils 328 8.2.1 Cucurbit[5]uril 328 8.2.2 Cucurbit[6]uril 331 8.2.3 Cucurbit[7]uril 339 8.2.4 Cucurbit[8]uril 346 8.2.5 Cucurbit[10]uril 351 viii Contents 8.3 Modification of Cucurbiturils 354 8.4 Uses of Cucurbiturils 361 8.5 Hemicucurbiturils 366 8.6 Conclusions 368 Bibliography 368 References 368 9 Rotaxanes and Catenanes 381 9.1 Introduction 381 9.2 Rotaxanes 382 9.2.1 Synthesis using statistical methods 382 9.2.2 Rotaxanes containing cyclodextrins, cucurbiturils and calixarenes 383 9.2.3 Rotaxanes based on π–electron interactions 388 9.2.4 Other synthetic methods for rotaxane synthesis 392 9.2.5 Rotaxanes as molecular machines 409 9.2.6 Thin films of rotaxanes 421 9.2.7 Polyrotaxanes 427 9.3 Catenanes 430 9.3.1 Synthesis using statistical and directed methods 431 9.3.2 Catenates and catenanes via metal templates 432 9.3.3 Catenanes based on π–electron interactions 450 9.3.4 Catenanes based on amide hydrogen-bonding interactions 474 9.3.5 Catenanes containing other macrocyclic units 479 9.3.6 Switchable catenanes 485 9.3.7 Catenanes on surfaces 493 9.3.8 Polycatenanes and catenated polymers 496 9.3.9 Natural catenanes 501 9.4 Conclusions 504 Bibliography 504 References 505 10 Other Supramolecular Systems, Molecular Motors, Machines and Nanotechnological Applications 518 10.1 Introduction 518 10.2 Other Molecular Systems 518 10.2.1 Aromatic and cyclacene compounds 518 10.2.2 Other cavitands 520 10.2.3 Pretzelanes, bonnanes and [1]rotaxanes 525 10.2.4 Trefoil knots 526 10.2.5 Solomon links and Borromean rings 539 10.2.6 Other systems 546 10.3 Molecular Devices, Motors and Machines 549 10.3.1 Molecular and supramolecular switches 550 10.3.2 Molecular motion 555 Contents ix 10.3.3 Light harvesting 565 10.3.4 Ion channels 566 10.3.5 Other uses of interlinked systems 567 10.4 Conclusions 567 Bibliography 570 References 570 Index 576 Preface The intention of this work is to serve as a detailed introduction to the field of macrocyclic chemistry.
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