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Stable Radicals Fundamentals and Applied Aspects of Odd-Electron Compounds Stable Radicals Fundamentals and Applied Aspects of Odd-Electron Compounds Editor ROBIN G. HICKS Department of Chemistry, University of Victoria, Canada A John Wiley and Sons, Ltd., Publication Stable Radicals Fundamentals and Applied Aspects of Odd-Electron Compounds Editor ROBIN G. HICKS Department of Chemistry, University of Victoria, Canada A John Wiley and Sons, Ltd., Publication Stable Radicals Fundamentals and Applied Aspects of Odd-Electron Compounds Editor ROBIN G. HICKS Department of Chemistry, University of Victoria, Canada A John Wiley and Sons, Ltd., Publication This edition first published c 2010 c 2010 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. 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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 Stable radicals : fundamentals and applied aspects of odd-electron compounds / editor, Robin G. Hicks. p. cm. Includes bibliographical references and index. ISBN 978-0-470-77083-2 (hardback) 1. Radicals (Chemistry) – Stability. 2. Electron mobility. I. Hicks, Robin G. QD471.S73 2010 541.224–dc22 2010010754 A catalogue record for this book is available from the British Library. ISBN 978-0-470-77083-2 Typeset in 10/12 Times by Laserwords Private Limited, Chennai, India Printed and bound in the United Kingdom by Antony Rowe Ltd, Chippenham, Wiltshire Contents Preface xv List of Contributors xvii 1. Triarylmethyl and Related Radicals 1 Thomas T. Tidwell 1.1 Introduction 1 1.1.1 Discovery of the triphenylmethyl radical 1 1.1.2 Bis(triphenylmethyl) peroxide 3 1.2 Free radical rearrangements 4 1.3 Other routes to triphenylmethyl radicals 5 1.4 The persistent radical effect 7 1.5 Properties of triphenylmethyl radicals 8 1.6 Steric effects and persistent radicals 9 1.7 Substituted triphenylmethyl radicals and dimers 9 1.8 Tris(heteroaryl)methyl and related triarylmethyl radicals 12 1.9 Delocalized persistent radicals: analogues of triarylmethyl radicals 14 1.10 Tetrathiatriarylmethyl (TAM) and related triarylmethyl radicals 16 1.11 Perchlorinated triarylmethyl radicals 20 1.12 Other triarylmethyl radicals 23 1.13 Diradicals and polyradicals related to triphenylmethyl 24 1.14 Outlook 28 Acknowledgements 28 References 28 2. Polychlorotriphenylmethyl Radicals: Towards Multifunctional Molecular Materials 33 Jaume Veciana and Imma Ratera 2.1 Introduction 33 2.2 Functional molecular materials based on PTM radicals 35 2.2.1 Materials with magnetic properties 37 2.2.2 Materials with electronic properties 53 2.2.3 Materials with optical properties 65 2.3 Multifunctional switchable molecular materials based on PTM radicals 69 2.3.1 Photo switchable molecular systems 69 2.3.2 Redox switchable molecular systems 70 2.4 Conclusions 75 References 76 vi Contents 3. Phenalenyls, Cyclopentadienyls, and Other Carbon-Centered Radicals 81 Yasushi Morita and Shinsuke Nishida 3.1 Introduction 81 3.2 Open shell graphene 82 3.3 Phenalenyl 84 3.4 2,5,8-Tri-tert-butylphenalenyl radical 86 3.5 Perchlorophenalenyl radical 92 3.6 Dithiophenalenyl radicals 94 3.7 Nitrogen-containing phenalenyl systems 97 3.7.1 Molecular design and topological isomers 97 3.7.2 2,5,8-Tri-tert-butyl-1,3-diazaphenalenyl 97 3.7.3 Hexaazaphenalenyl derivatives 102 3.7.4 β-Azaphenalenyl derivatives 103 3.8 Oxophenalenoxyl systems 106 3.8.1 Molecular design and topological isomers 106 3.8.2 3-Oxophenalenoxyl (3OPO) system 108 3.8.3 4- and 6-Oxophenalenoxyl (4OPO, 6OPO) systems 110 3.8.4 Redox-based spin diversity 114 3.8.5 Molecular crystalline secondary battery 115 3.8.6 Spin-center transfer and solvato-/thermochromism 117 3.9 Phenalenyl-based zwitterionic radicals 119 3.10 π-Extended phenalenyl systems 122 3.10.1 Triangulenes 122 3.10.2 Trioxytriangulene with redox-based spin diversity nature 125 3.10.3 Bis- and tris-phenalenyl system and singlet biradical characters 125 3.11 Curve-structured phenalenyl system 130 3.12 Non-alternant stable radicals 131 3.12.1 Cyclopentadienyl radicals 131 3.12.2 Cyclopentadienyl radicals within a larger π-electronic framework 135 3.13 Stable triplet carbenes 136 3.14 Conclusions 139 Acknowledgements 139 References 140 4. The Nitrogen Oxides: Persistent Radicals and van der Waals Complex Dimers 147 D. Scott Bohle 4.1 Introduction 147 4.2 Synthetic access 149 4.3 Physical properties 149 4.4 Structural chemistry of the monomers and dimers 150 4.4.1 Nitric oxide and dinitrogen dioxide 150 4.4.2 Nitrogen dioxide and dinitrogen tetroxide 152 4.5 Electronic structure of nitrogen oxides 153 4.6 Reactivity of nitric oxide and nitrogen dioxide and their van der Waals complexes 155 4.7 The kinetics of nitric oxide’s termolecular reactions 156 4.8 Biochemical and organic reactions of nitric oxide 158 Contents vii 4.9 General reactivity patterns 160 4.9.1 Oxidation 160 4.9.2 Reduction 161 4.9.3 Coordination 162 4.9.4 Addition of nucleophiles 162 4.9.5 General organic reactions 165 4.9.6 Reactions with other nucleophiles 165 4.10 The colored species problem in nitric oxide chemistry 166 4.11 Conclusions 166 References 166 5. Nitroxide Radicals: Properties, Synthesis and Applications 173 Hakim Karoui, Franc¸ois Le Moigne, Olivier Ouari and Paul Tordo 5.1 Introduction 173 5.2 Nitroxide structure 174 5.2.1 Characteristics of the aminoxyl group 174 5.2.2 X-ray structures of nitroxides 175 5.2.3 Quantum mechanical (QM), molecular dynamics (MD) and molecular mechanics (MM) calculations 177 5.2.4 Influence of solvent polarity on the EPR parameters of nitroxides 180 5.3 Nitroxide multiradicals 181 5.3.1 Electron spin–spin exchange coupling 182 5.3.2 Miscellaneous aspects of di- and polynitroxides 184 5.4 Nitronyl nitroxides (NNOs) 185 5.4.1 Synthesis of nitronyl nitroxides 186 5.4.2 Nitronyl nitroxide as a nitric oxide trap 186 5.4.3 Nitronyl nitroxides as building blocks for magnetic materials 188 5.5 Synthesis of nitroxides 191 5.5.1 Oxidation of amines 191 5.5.2 Oxidation of hydroxylamines 191 5.5.3 Chiral nitroxides 191 5.5.4 Nitroxide design for nitroxide mediated polymerization (NMP) 193 5.6 Chemical properties of nitroxides 196 5.6.1 The Persistent Radical Effect 197 5.6.2 Redox reactions 197 5.6.3 Approaches to improve the resistance of nitroxides toward bioreduction 198 5.6.4 Hydrogen abstraction reactions 199 5.6.5 Cross-coupling reactions 200 5.6.6 Nitroxides in synthetic sequences 200 5.7 Nitroxides in supramolecular entities 206 5.7.1 Interaction of nitroxides with cyclodextrins 207 5.7.2 Interaction of nitroxides with calix[4]arenes 209 5.7.3 Interaction of nitroxides with curcubiturils 210 5.7.4 Interaction of nitroxides with micelles 211 5.7.5 Fullerene-linked nitroxides 212 viii Contents 5.8 Nitroxides for dynamic nuclear polarization (DNP) enhanced NMR 213 5.8.1 DNP for biological NMR and real-time metabolic imaging 213 5.8.2 Nitroxides as polarizing agents for DNP 214 5.9 Nitroxides as pH-sensitive spin probes 216 5.10 Nitroxides as prefluorescent probes 217 5.11 EPR-spin trapping technique 217 5.11.1 Immuno spin trapping 219 5.11.2 Conclusion 219 5.12 Conclusions 220 References 220 6.
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