Table Of ContentElectron Spin Resonance
Volume IOA
A Specialist Periodical Report.
Electron Spin Resonance
Volume IOA
A Review of Recent Literature
Senior Reporter
M. C. R. Symons, Department of Chemistry,
University of L ekes ter
Reporters
Ching-San Lai, Medical College of Wisconsin, Milwaukee, U.S. A.
N. J. F. Dodd, Christie Hospital, Manchester
W. Froncisz, Jagiellonian University, Krakow, Poland
D. J. T. Hill, University of Queensland, Brisbane, Australia
A. Hudson, University of Sussex
J. S. Hyde, Medical College of Wisconsin, Milwaukee, U.S.A.
T. J. Kemp, University of Warwick
J. H. O’Donnell, University of Queensland, Brisbane, Australia
P. J. Pomery, University of Queensland, Brisbane, Australia
B. J. Tabner, University of Lancaster
The Royal Society of Chemistry
Burlington House, London, WIV OBN
ISBN 0-85186-841-X
ISSN 0305-9578
Copyright 0 1986
The Royal Society of Chemistry
All Rights Reserved
No part of this book may be reproduced or transmitted
in any form or by any means - graphic, electronic,
including photocopying, recording, taping or
information storage and retrieval systems without
-
written permission from The Royal Society of Chemistry
Printed in Great Britain at the Alden Press, Oxford,
London and Northampton
Foreword
There have been several changes in this SPR since Volume 9 appeared. The most
significant is that Professor Peter Ayscough, who has guided us through the last
6 volumes so skillfully, decided to resign, and I have been asked to take over.
Thus my first, and most important, task is to offer our collective vote of
thanks to Peter for all his efforts during these years.
I found at once that this was not just a simple matter of 'changing hands.'
In fact, all the Specialist Periodical Reports of the Royal Society of Chemistry
are under threat, since, on average, they have been running at a serious loss
and I was faced with the task of trying to pull the ESR Volume above the cut-off
line. This is one reason for the split into Volumes 10A and 10B, the former
(present) volume being largely concerned with Organic and Bio-organic e.s.r.,
and the latter (B) being largely concerned with Inorganic and Bio-inorganic
topics. Our aim has been to produce these Volumes so that they are available at
the International Conferences under these headings which are held every Spring
under the auspices of the Royal Society for Chemistry. With a financial
incentive to buy at the Conference we very much hope that these valuable books
will be purchased by many, in order to ensure their continuation - so please
help.
As in past years, each Volume has as its kernal the main developments in the
major chemical and biochemical areas of e.s.r. However, from time to time we
plan to carry special articles on instumental developments and on topics of
peripheral interest (such as muon spin resonance, for example). In this issue
there is a very welcome article on 'loop-gap resonators' which fits into this
category.
I am most grateful to all the authors for meeting my dead-line and for
producing such valuable contributions and to the Society for ensuring public-
ation in time for the ESR Spring Meeting.
Martyn C. R. Syrnons
Cont ents
CHAPTER 1 Organic Radicals in Solution
By B.J. Tabner
1 Introduction 1
2 Carbon-centered Radicals 2
3 Nitrogen-centered Radicals 12
4 Oxygen-centered Radicals 13
5 Nitroxides 14
6 Sulphur-centered Radicals 16
7 Radical Cations 17
8 Radical Anions 28
9 CIDEP 34
References 36
CHAPTER 2 Organic Radicals in Solids
By T.J. Kemp
1 Introduction and Bibliography 42
2 Technical, Analytical and Theoretical Developments 43
3 Spectroscopic Aspects 45
3.1 Alkane Radical Cations 45
3.2 Radical Cations from Aliphatic Compounds 46
3.3 Radical Cations from Aromatic Compounds 50
3.4 Radical Anions 51
3.5 Neutral Radicals 52
4 Mechanistic Studies 53
5 Molecules of Biological Interest 60
6 Radicals at Surfaces and Semi-conductors 62
References 63
vii
viii Con ten rs
CHAPTER 3 Triplets and Biradicals
By A. Hudson
1 Introduction 66
2 Triplets and Radical Pairs in Fluid Solution 66
3 Ground and Thermally Excited Triplets, Quintets and Nonets 67
4 Photoexcited Triplets 71
5 Photoexcited Biomolecules 75
6 Excitons and Energy Migration 78
Iieferences 80
CHAPTER 4 Applications of ESR in Polymer Chemistry
By D.J.T. Hill, J.H. O'Donnell, and P.J. Pornery
1 Introduction 84
2 Polymer Degradation 85
2.1 Ionizing Radiation 85
2.1.1 Polyolefins 86
2.1.2 Fluorinated Polymers 87
2.1.3 Vinyl Polymers 88
2.1.4 Polyamides and Other Polymers 88
2.1.5 Cellulose 89
2.1.6 Electron Resists 89
2.2 Photodegradation 90
2.2.1 Polyolefins 90
2.2.2 Vinyl Polymers 91
2.2.3 Polyamides, etc. 91
2.2.4 Specialized Polymers 92
2.2.5 Surface Coatings 92
2.3 Mechano-chemical Degradation 93
2.3.1 Polyolefins and Vinyl Polymers 93
2.3.2 Polyamides 94
2.3.3 Other Polymers 94
3 Polymerization 95
3.1 Initiation of Polymerization 95
3.2 Homogeneous Chain Growth 97
3.2.1 Solid State Polymerizations 97
3.2.2 Liquid State Polymerization 100
3.2.3 Resins, Composites and Coatings 101
3.3 Heterogeneous Chain Growth 102
3.3.1 Graft Polymerization 102
3.3.2 Plasma Polymerization 103
3.3.3 Polymerization Catalysts 103
4 Polymer Structure 104
4.1 Spin Probes and Spin Labels 104
4.1.1 Polyolefins 105
4.1.2 Vinyl Polymers 106
4.1.3 Poly(ethy1ene oxide) 108
