Solid-State NMR I Methods

285 Pages·1994·9.015 MB·English

by  Arnd-Rüdiger Grimmer, Bernhard Blümich (auth.), Prof. Dr. Bernhard Blümich (eds.)

NMR
30
Basic Principles and Progress
Editors: P. Diehl E. Fluck H. Gunther
R. Kosfeld J. Seelig
Advisory Board: G. Bodenhausen S. Forsen
R. K. Harris C. L. Khetrapal T. E. Lippmaa
G. J. Martin H. Pfeifer A. Pines B. L. Shapiro
Solid-State NMR I
Methods
Guest-Editor: B. Bliimich
With contributions by
B. BIUmich, P. BIUmler, B.F. Chmelka,
G. Fleischer, F. Fujara, A.-R. Grimmer,
F. Laupretre, D. Raftery
With 141 Figures and 10 Tables
Springer-Verlag
Berlin Heidelberg New York
London Paris Tokyo
Hong Kong Barcelona Budapest
ISBN-13 : 978-3-642-78485-9 e-ISBN-13 : 978-3-642-78483-5
DOl: 10.1007/978-3-642-78483-5
This work is.subject to copyright. All rights are reserved, whether the whole or part of the
material is concerned, specifically the rights of translation, reprinting, reuse of illustrations,
recitation, broadcasting, reproduction on microfilm or in any other way, and storage in data
banks. Duplication of this publication or parts thereof is permitted only under the provisions
of the German Copyright Law of September 9, 1965, in its current version, and permission
for use must always be obtained from Springer-Verlag. Violations are liable for prosecution
under the German Copyright Law.
© Springer-Verlag Berlin Heidelberg 1994
Softcover reprint of the hardcover 1st edition 1994
Library of Congress Catalog Card Number 93-9522
The use of general descriptive names, registered names, trademarks, 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.
Product liability: The publishers cannot guarantee the accuracy of any information about
dosage and application contained in this book. In every individual case the user must check
such information by consulting the relevant literature.
Typesetting: Thomson Press (India) Ltd, New Delhi
5113020 - 543210 - Printed on acid-free paper
Preface
Solid-State NMR is a branch of Nuclear Magnetic Resonance which
is presently experiencing a phase of strongly increasing popularity.
The most striking evidence is the large number of contributions from
Solid-State Resonance on NMRmeetings, approaching thatofliquid
state Resonance. Important progress can be observed in three areas:
Methodical developments, applications to inorganic matter, and
applications to organic matter. These developments are intended to
be captured in three volumes of this series, each of them being
devoted to more or less one of these areas.
The present volume on Solid-State NMR I is devoted largely to
methodical aspects. The fIrst chapter provides an introduction which
reviews some of the basic features of Solid-State spectroscopy. The
second chapter demonstrates methods and application of high
resolution 13C-NMR for the study of local dynamics in polymers.
Chapter three reviews xenon NMR as a tool for the characterization
of complex chemical systems and host phases. Chapter four covers
translational diffusion NMR in analogy to generalized incoherent
scattering experiments, a topic which promises to become of great
value also in Solid-State research. The last chapter reviews the
developments of methods for acquisition of NMR information in
solids with spatial resolution.
Of course, the topics chosen in all three Solid-State NMR volumes
by no means cover the entire area of Solid-State NMR, but it is hoped
thatthey treat an attractive cross-section of today's research. Particular
thanks goes to the authors for their pleasant cooperation and, most
importantly, for writing the contributions. Springer-Verlag has been
very helpful in its assistance and editorial supervision.
Aachen, August 1993 B.Blumich
R. Kosfeld
Guest-Editor
Prof. Dr. Bernhard Blumich
Lehrstuhl fur Makromolekulare Chemie,
RTWH Aachen, Worringer Weg 1,
D-52056 Aachen, FRG
Editorial Board:
Prof. Dr. Peter Diehl Instihlt fiIr Physik der Universitlit Basel, KJingelbergstraBe 82,
CH-4056 Basel
Prof. Dr. Ekkehard Fluck Gmelin-Instihlt, VarrentrappstraBe 40/42,
0-60486 Frankfurt am Main, FRG
Prof. Dr. H. GUnther Universitlit SiegeD, Organische Chemie IT,
Postfach 101240,0-57076 Siegen, FRG
Prof. Dr. Robert Kosfeld In den Atzenbenden 30, 0-52080 Aachen, FRG
Prof. Dr. J. Seelig Biozentrum der Universitlit Basel, Abt Biophysikalische
Chemie, KJingelbergstraBe 70, CH-4056 Basel
Advisory Board:
Prof. Dr. Section de chimie, Universite de Lausanne,
Geoffrey Bodenhausen Rue de la Barre 2, CH-l005 Lausanne
Prof. Dr. Sturse Forsen Department ofP hysical Chemistry; Chemical Centre,
University of Llmd, P.O.B. 740, S-22007 Lund
Prof. Dr. Robin K. Harris University of Durham, Department of Chemistry,
Science Laboratories, South Road, GB-Durham DH13LE
Prof. Dr. C. L Khetrapal Sophisticated Instruments Facility, Indian Instihlte of Science,
Bangalore-560 012, India
Prof. Dr. T. E. LippmtUl InstihlteofChemical Physics and Biophysics,
Academy of Sciences of the Estonian SSR, Lenini paiestee 10,
Tallinn 200001, Estonia
Prof. Dr. G. J. Martin Universite de Nantes, U.E.R. de Chimie,
Resonance Magnetique Nucleaire el Reactivite Chimique,
UA-CNRS No 472, 2, rue de la Houssiniere,
F-44072 Nantes Cedex
Prof. Dr. Harry Pfeifer Fachbereich Physik, Universitlit Leipzig, UnnestraBe 5,
0-04103 Leipzig, FRG
Prof. Dr. Alex Pines University of California, Berkeley, Department of Chemistry,
Berkeley, CA 94720, USA
Prof. Dr. Bernard 1.. Shapiro 966 Elsinore Court, Palo Alto, CA 94303, USA
Table of Contents
Introduction to Solid·State NMR
A.-R. Grimmer, B. Bliimich . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
High·Resolution 13C NMR Investigations of Local
Dynamics in Bulk Polymers at Temperatures Below
and Above the Glass Transition Temperature
F. Laupretre . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 63
Xenon NMR Spectroscopy
D. Raftery, B.F. Chmelka ........................... 111
NMR as a Generalized Incoherent Scattering Experiment
G. Fleischer, F. Fujara . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 159
NMR Imaging of Solids
P. Bliimler, B. Bliimich ............................... 209
Author Index Volumes 21·3 ......................... 279
Table of Contents of Volume 31
Solid-State NMR II - Inorganic Matter
29Si NMR of Inorganic Solids
G. Engelhardt and H. Koller
NMR of Solid Surfaces
H. Pfeifer
MAS and CP/MAS NMR of Less Common
A. Sebald
Satellite Transition Spectroscopy of Quadrupolar
Nuclei
C. Jager
NMR-NQR Studies of High-Temperature
Superconductors
D. Brinkmann and M. Mali
Introduction to Solid-State NMR
Arnd-Riidiger Grimmer! and Bernhard B1iimich2
1 Projektgruppe Festkorper-NMR in KAI e.V., Rudower Chaussee 5, Haus 4.1, D-12489 Berlin
Adlershof, FRG
2 Lehrstuhl fiir Makromolekulare Chemie, RWTH Aachen, Worringerweg 1, D-52074 Aachen, FRG
Table of Contents
1 Introduction 3
2 Principles of NMR . . . . 4
2.1 The NMR Phenomenon 4
2.1.1 Zeeman Interaction 5
2.1.2 Population Differences 7
2.1.3 Relaxation . . . . 8
2.2 Spin Interactions in the Solid State 9
2.2.1 Types of Interaction 9
2.2.2 General Formalism: Magnetic Shielding 10
2.2.3 Magnetic Shielding: Experimental Aspects 14
2.2.4 Dipole-Dipole Coupling 19
2.2.5 Quadrupolar Coupling 23
3 NMR Spectroscopy .... 28
3.1 High-Resolution NMR . . 28
3.1.1 Magic-Angle Spinning 29
3.1.2 Heteronuclear High-Power Decoupling 35
3.1.3 Multipulse Techniques . . . . . . 36
3.1.4 CRAMPS ......... . 38
3.1.5 Magnetic Dilution: "Chemical" Decoupling 38
3.1.6 Cross-Polarization 39
3.2 Wide-Line NMR . . . . . 42
3.2.1 Molecular Order 43
3.2.2 Molecular Reorientation 49
4 Imaging 54
5 References 59
NMR Basic Principles and Progress, Vol. 30
© Springer-Verlag, Berlin Heidelberg 1994
2 A.-R. Grimmer and B. Bliimich
Solid-state NMR spectra generally reflect the sum of several independent interactions such as
Zeeman, dipolar and quadrupolar coupling as well as magnetic shielding effects. To obtain the
desired information, separation of these effects and their decoding is essential. Within the first part,
as a basis of the successful separation of the NMR effects, the common and also the different
(tensorial) properties of each interaction are discussed in detail. The second part mainly deals with
the experimental design of solid-state high-resolution NMR experiments to suppress certain
interactions and with wide-line experiments. Finally the principles of NMR imaging and NMR
microscopy are described as an alternative method for investigating solids by NMR.
Introduction to Solid-State NMR 3
1 Introduction
Solids have always assumed a substantial role in development of human culture,
from the very beginning in the Stone Age-named after predominantly
siliceous solids-until the present period of sophisticated materials. Depending
on their wide range of structure, solids exhibit specific mechanical, thermal,
electric, magnetic, optic, and, last but not least, biological properties. The
knowledge of these structures in the widest sense is an essential condition for
their proper economic and ecological use. Among the physical methods contri
buting to this knowledge, solid-state NMR is now established as a technique
with widespread applications.
The first NMR experiments were carried out in 1945 on solid paraffin [1a]
as well as on liquid water [1b]. Immediately followed by investigations of
dipolar interactions in solids [2], which created the basis of wide-line NMR.
Due to restrictions imposed by effects of the dipole-dipole couplings, however,
these early experiments were of limited value, with investigations of dynamic
processes in polymers being one possible exception. The same is valid for
quadrupolar effects· [3], although studies of inorganic glasses [4] should be
mentioned as a positive example for wide-line NMR.
A little later, the discovery of chemical shift [5,6] and indirect dipolar
coupling [7] marked the starting point of dynamic growth of the still young
technique. Due to the more or less convenient accessibility of these parameters
in liquids most of the work following has been devoted to liquid-state NMR.
During the 1950s and the 1960s the condition of solid-state NMR was defined
by the generally accepted statement [8, 9] that chemical shift is not detectable
in solids. Contrasting this pessimism, singular examples of wide-line measure
ments of chemical shifts in solids (Fig. 1) seemed to bear the message of an
imminent vigorous development.
oI I
100 -\00 -200 -300 ppm
Fig. 1. 31p CW NMR spectrum of PCls at 24 MHz (static sample, first derivative spectrum). The
two 1: 1 signals reflect the structure as ionic PCI PCI [26]
4 6