Springer Series in Materials Science 292 Gertz I. Likhtenshtein Nitroxides Brief History, Fundamentals, and Recent Developments Springer Series in Materials Science Volume 292 Series Editors Robert Hull, Center for Materials, Devices, and Integrated Systems, Rensselaer Polytechnic Institute, Troy, NY, USA Chennupati Jagadish, Research School of Physical, Australian National University, Canberra, ACT, Australia Yoshiyuki Kawazoe, Center for Computational Materials, Tohoku University, Sendai, Japan Jamie Kruzic, School of Mechanical & Manufacturing Engineering, UNSW Sydney, Sydney, NSW, Australia Richard M. Osgood, Department of Electrical Engineering, Columbia University, New York, USA Jürgen Parisi, Universität Oldenburg, Oldenburg, Germany Udo W. Pohl, Institute of Solid State Physics, Technical University of Berlin, Berlin, Germany Tae-Yeon Seong, Department of Materials Science & Engineering, Korea University, Seoul, Korea (Republic of) Shin-ichi Uchida, Electronics and Manufacturing, National Institute of Advanced Industrial Science and Technology, Tsukuba, Ibaraki, Japan Zhiming M. Wang, Institute of Fundamental and Frontier Sciences - Electronic, University of Electronic Science and Technology of China, Chengdu, China The Springer Series in Materials Science covers the complete spectrum of materials research and technology, including fundamental principles, physical properties, materials theory and design. Recognizing the increasing importance of materials science in future device technologies, the book titles in this series reflect the state-of-the-art in understanding and controlling the structure and properties of all important classes of materials. More information about this series at http://www.springer.com/series/856 Gertz I. Likhtenshtein Nitroxides Brief History, Fundamentals, and Recent Developments 123 Gertz I. Likhtenshtein Department of Chemistry Ben-Gurion University of the Negev Beersheba, Israel Institute of Problems of Chemical Physics Russian Academy of Science Chernogolovka, Moscow Region, Russia ISSN 0933-033X ISSN 2196-2812 (electronic) Springer Series in Materials Science ISBN 978-3-030-34821-2 ISBN 978-3-030-34822-9 (eBook) https://doi.org/10.1007/978-3-030-34822-9 © Springer Nature Switzerland AG 2020 This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission or information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar methodology now known or hereafter developed. The use of general descriptive names, registered names, trademarks, service marks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. The publisher, the authors and the editors are safe to assume that the advice and information in this book are believed to be true and accurate at the date of publication. Neither the publisher nor the authors or the editors give a warranty, expressed or implied, with respect to the material contained herein or for any errors or omissions that may have been made. The publisher remains neutral with regard to jurisdictional claims in published maps and institutional affiliations. This Springer imprint is published by the registered company Springer Nature Switzerland AG The registered company address is: Gewerbestrasse 11, 6330 Cham, Switzerland Preface It is known that there are delicate links and fine parallels between an art and science. Both these spheres of human endeavor involve a unique combination of profes- sional skill and creative search. Sometimes, an intuitive line of a great poet or philosopher may be likened to the opening of a new horizon in science. Thus, the composer Maurice Ravel in his famous “Bolero” allegorically depicts the process of birth and development of an epochal discovery that gives rise to many advantages. Like that opening musical movement, the first publication on synthesis a nitroxide by Fremi in 1825 initiated, after a long lag period, the birth and rapid development of a novel class of stable nitroxide radicals which happened to be extremely important in both aspects, basic and applied. At present, the science of nitroxides widely extended her “hands” to chemistry, physics, and biology. The application of nitroxides ranges from use as spin labels and antioxidants in biological studies, charge carriers for energy storage, basis for magnetic materials' mediators in polymerization reactions, functional spin probes for pH, oxygen, and thiol levels to catalysts in chemical and electrochemical oxi- dation reactions. Classical and modern physical chemistry and chemical physics, chemical kinetics, organic, inorganic, and quantum chemistry provide an arsenal of physical methods and establish a basis for the investigation of structure and action mecha- nism of processes involving nitroxides. This book embraces all principal aspects of structure and physicochemical action mechanisms of nitroxides. It is a view of nitroxides by a physicochemist with long-term experience in the area. The book is not intended to provide an exhaustive survey of each topic but rather a discussion of their theoretical and experimental background and recent developments. The literature of nitroxides is so vast, and many scientists have made important contribution in the area that it is impossible in the space allowed for this book to give a representative set of references. In fact, for each section in this area one can write several books. The author apologizes to those he has not been able to include. v vi Preface Research on nitroxide which combines their fundamental importance for human welfare and intellectual fascination for investigation will promote solving exciting and complicated problems in chemistry, biology, and physics. Chapter 1 of the monograph is a brief outline of 175 years history of nitroxides. Chapters 2 and 3 form the theoretical and experimental chemical background for nitroxide numerous application. Chapter 4 is a general survey of fundamentals of electron spin resonance and nuclear magnetic resonance, and main physical methods directly related to nitroxide. Advantages in design and use of nitroxide biradicals are reviewed in Chap. 5. Chapter 6 presents a review on the use of tethered nitroxide–fluorophore molecules as probes of redox status, antioxidant activity, oxidative stress, and free radical reaction. Nitroxide-mediated polymer- ization (NMP) is the subject of Chap. 7. Chapter 8 describes role nitroxides as the base for magnetic materials. Involving nitroxide radicals and their derivatives in biological processes is in focus of Chap. 9. Applications of nitroxides as spin labels and probes constitute the contents of Chap. 10. Chapter 11 is devoted to the use of nitroxyls to solve some of the physicochemical problems. The monograph is intended for scientists and engineers working in the fields of chemistry, physics, and biology in which nitroxyls currently find or would find their application. Book, as a whole, and separate chapters can be used as a subsidiary manual for instructors, graduate and undergraduate students of university chem- istry, physics, and biophysics departments. Department of Chemistry, Ben-Gurion University of the Negev and Institute of Problem of Chemical Physics, Russian Academy of Science provided excellent conditions for writing this book for which the author is extremely grateful. Moscow Region, Russia/Beersheba, Israel Gertz I. Likhtenshtein Contents 1 Nitroxides: 170 Years of History ........................... 1 1.1 Long Preamble of a Tale (1845–1960) ................... 1 1.2 “Golden” Decade (1962–1972) ........................ 3 1.3 New Era ......................................... 8 1.4 Concluding Remarks ................................ 12 References ............................................ 14 2 Nitroxide Basic Physical Properties ......................... 21 2.1 Introduction ...................................... 21 2.2 Spin Electron–Spin Nuclear Interactions in Nitroxides........ 23 2.3 Relationships Between the Structure and Properties of Nitroxide ...................................... 25 References ............................................ 33 3 Nitroxide Chemical Reactions ............................. 35 3.1 Introduction ...................................... 35 3.2 Nitroxide Redox Potential ............................ 36 3.3 Oxoammonium Cation Reactions ....................... 42 3.4 Nitroxide Cross-Coupling Reactions ..................... 47 3.5 Nitroxides in Electrocatalysis .......................... 50 3.6 Nitroxides as Radical Scavenger ....................... 54 3.7 Nitroxide Reaction with Typical Antioxidants.............. 58 3.8 Nitroxide Redox Behavior in Biological Systems ........... 63 References ............................................ 65 4 ESR and NMR as Tools for Nitroxides Studies ................ 71 4.1 Introduction ...................................... 71 4.2 Spin Electron–Spin Electron Interactions. Distance Determination ..................................... 73 4.2.1 Spin Electron–Spin Nuclear Interactions ........... 82 References ............................................ 88 vii viii Contents 5 Nitroxide Biradicals .................................... 93 Alexander I.