Magnetic Molecular Materials

412 Pages·1991·27.485 MB·English

by  Fernando Palacio (auth.), Dante Gatteschi, Olivier Kahn, Joel S. Miller, Fernando Palacio (eds.)

Magnetic Molecular Materials
NATO ASI Series
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Series E: Applied Sciences - Vol. 198
Magnetic Molecular Materials
edited by
Dante Gatteschi
University of Florence, Florence, Italy
Olivier Kahn
University of Paris Sud, Orsay, France
Joel S. Miller
Du Pont, Wilmington , Delaware, U.S.A.
and
Fernando Palacio
CSIC, Universit y of Zaragoza, Zaragoza, Spain
k4
Springer Science+Busines sMedia, B.V.
Proceeding s of the NATO Advanced Research Workshop on
Magnetic Molecular Materials
"II Ciocco" , Castelvecchi o Pascoli, Lucca, Italy
28 October - 2 November 1990
Library of Congress Cataloging-in-Publicatio n Data
Magnetic Molecula r material s / edite d by Dante Gattesch i .. . (e t a!.J .
p. en. — (NATO ASI series . Serie s E. Applie d science s ;
vol. 198)
Papers fro n th eN ATO Advanced Research Workshop on "Magneti c
Molecular Materials" , hel d Oct. 28-Nov. 2, 1990, i n I I Ciocco .
Italy ; sponsore d by th eN ATO Scientifi c Affair s Division .
Include s Index .
ISBN 978-94-010-5435-5 ISBN 978-94-011-3254-1 (eBook)
DOI 10.1007/978-94-011-3254-1
1. Magneti c materials—Congresses . 2. Materials—Magneti c
properties—Congresses . 3. Molecula r dynamics—Congresses.
I. Gatteschi , 0. (Dante ) II . NATO Advanced Research Workshop on
"Magneti c Molecula r Materials " (199 0 : I I Ciocco , Italy )
III . Nort h Atlanti c Treat y Organization . Scientifi c Affair s
Division . IV . Series : NATO ASI series . Serie s E. Applie d science s
: no. 198
0C764.5.M34 1991
538*.4—dc20 91-1299 5
ISBN 978-94-010-5435-5
Printed on acid-free paper
All Rights Reserved
© 1991 Springer Science+Busines s Media Dordrecht
Originally published by Kluwer Academic Publisher s in 1991
Softcover reprint of the hardcover 1st edition 1991
No part of the material protected by this copyrigh t notice may be reproduce d or
utilized in any form or by any means, electroni c or mechanical , includin g photo-
copying , recordin g or by any informatio n storage and retrieval system, without written
permissio n from the copyrigh t owner.
CONTENTS
LECTURES
FROM FERROMAGNETIC INTERACTIONS TO MOLECULAR
FERROMAGNETS: AN OVERVIEW OF MODELS AND
MATERIALS . 1
F. Palacio
DESIGN OF MOLECULAR-BASED COMPOUNDS EXHIBITING
A SPONTANEOUS MAGNETIZATION; STRATEGIES AND
ACHIEVEMENTS .35
O. Kahn
AN APPROACH TO ORGANIC FERROMAGNETS. SYNTHESIS
AND CHARACTERIZATION OF POLYMERS DUE TO
1-PHENYL-1,3-BUTADYINES CARRYING ASUBSTITUENT IN
DOUBLET ORTRIPLET STATE ON THE PHENYL RING .53
H. Iwamura, S. Sasaki, N. Sasagawa, K. Inoue, N. Koga
MAGNETIC COUPLING IN HIGH SPIN CARBENES .67
K.Itoh
INTERMOLECULAR FERROMAGNETIC COUPLING IN
ORGANIC RADICAL CRYSTALS .87
M. Kinoshita
APPROACHES TO MAGNETIC ORGANIC MATERIALS .105
D.A. Dougherty, R.H. Grubbs, D.A. Kaisaki, W. Chang, S.J. Jacobs,
D.A. Shultz, K.K. Anderson, R. Jain, P.T. Ho, E.G. Stewart
STABLE POLYRADICALS WITH HIGH SPIN GROUND STATES .121
J. Veciana, C. Rovira
SUPERDEGENERACIES AND ORBITALDELOCALIZATION IN
EXTENDED ORGANIC SYSTEMS .133
T. Hughbanks, K.A. Yee
vi
MAGNETISM OF RADICAL CATION SALTS BASED ON THE
ORGANIC DONORTETRAMETHOXY-HEXA-META-
PHENYLENE .145
T. Bjornholm, K. Bechgaard, P. Sommer-Larsen, G. Rindorf, N.
Thorup
RECENT ADVANCES IN THE STRUCTURE-MAGNETIC
COUPLING RELATIONSHIP FORMETALLOCENE-ACCEPTOR
BASED ELECTRON TRANSFER COMPLEXES .151
J.S. Miller, A.J. Epstein
PHYSICS OF THE 1-D MOLECULAR FERROMAGNET
DECAMETHYLFERROCENIUM TETRACYANOETHANIDE,
[DMeFcl+[TCNE1-. .159
A. J. Epstein, J. S. Miller
MODELS FORMAGNETIC COUPLING IN METALLOCENE
BASED DONOR ACCEPTOR COMPLEXES .171
D.A. Dixon, A. Suna, J.S. Miller, A.J. Epstein
MAGNETIC PROPERTIES OF SOME BIRADICALS OF D2d (OR
APPROXIMATE D2d) SYMMETRY, EXTENDED-DIOXYGEN
ANALOGS . . .191
A. Rassat, R. Chiarelli
COORDINATION CHEMISTRY OF THE IMINO NITROXIDES.
FERROMAGNETIC BEHAVIOR OF SOME FIRST ROW
TRANSITION METAL COMPLEXES .203
P. Rey, D. Luneau, A. Cogne
STRUCTURAL MAGNETIC CORRELATIONS IN PHASE
TRANSITIONS OF MOLECULAR MAGNETS .215
A. Caneschi, D. Gatteschi, R. Sessoli
MAGNETIC MOLECULAR MATERIALS CONTAINING RARE
EARTHS .233
C. Benelli, A. Caneschi, D. Gatteschi, L. Pardi
MAGNETISM OF LIQUID CRYSTALS .245
W. Haase, R. Borchers
vii
MOLECULAR FERROMAGNETISM IN ORGANIC AND
INORGANIC COMPLEXESj INFLUENCE OF ORBITAL
EFFECTS .255
M. Drillon, J. L. Paillaud, P. Legoll
THE EDTAFAMILY OF MOLECULARBASED
FERROMAGNETS .267
E. Coronado
TOWARDS HIGH Tc FERRO AND FERRIMAGNETIC BI AND
TRIDIMENSIONAL MATERIALS FROM MOLECULAR
PRECURSORS .281
V. Gadet, M. Bujoli-Doeuff, L. Force, M. Verdaguer, K. EI Malkhi,
A. Deroy, J. P. Besse, C. Chappert, P. Veillet, J. P. Renard, P.
Beauvillain
HIGH SPIN INORGANIC CLUSTERS: SPIN FRUSTRATION IN
POLYNUCLEAR MANGANESE AND IRON COMPLEXES .2~7
J. K. McCusker, E. A. Schmitt, D. N. Hendrickson
EXCHANGE INTERACTIONS IN MOLECULAR SOLIDS .321
R. Georges
MAGNETIC AND OPTICAL EXCITATIONS IN CLUSTERS .333
H. U. Giidel
FREQUENCY DEPENDENT SUSCEPTIBILITIES OF
MAGNETIC MATERIALS .353
A.J. van Duyneveldt
SPIN DENSITY OF THE NITROXIDE FREE RADICALS 4.0L
AND 4.0XO 2,2,6,6 TETRAMETHYL PIPERIDYL 1-0XYL:
TANOL AND TANO .371
D. Bordeaux, J.X. Boucherle, B. Delley, B. Gillon, E. Ressouche, J.
Schweizer
viii
REPORTS ONROUND TABLES
THE DESIGN STRATEGIES .385
O. Kahn, D.N. Hendrickson, H. Iwamura, J. Veciana
PHYSICALINVESTIGATION ON MAGNETIC MOLECULAR
MATERIALS. .389
F. Palacio, R. L. Carlin, A. J. van Duyneveldt, A. J. Epstein, H. U.
Glidel, C. P. Landee, J. Schweizer
MOLECULARMAGNETIC MATERIALS. APPLICATIONS .395
C. P. Landee, D. Melville, J. S. Miller
PARTICIPANTS .399
INDEX .401
PREFACE
One of the major challenges of science in the last few years of the second
millenniumislearninghow to design materials whichcanfulfill specifictasks. Ambitious
as it may be, the possibilities ofsuccess are not ne~li~ble provided that all the different
expertises merge to overcome the limits of eXIsting disciplines and forming new
paradigms science.
The NATO Advanced Research Workshop on "Magnetic Molecular Materials"
wasorganizedwiththeaboveconsiderationsin mindinorder to determinewhich are the
most appropriate synthetic strategies, experimental techniques of investigation, and
theoretical models which are needed in order to develop new classes of magnetic
materials whicharebasedonmolecules rather thanonmetallicorioniclattices.
Why molecules? The answer may be obvious: molecular chemistry in principle
fine can tune the structures and the properties of complex aggregates, and nature
already provides a large number of molecular aggregates which can perform the most
disparatefunctions.
The contributions collected in this book provide a rather complete view of the
current research accomplishments of magnetic molecular materials. There are several
different synthetic approaches which are followed ranging from purely organic to
inorganic materials. Some encouraging successes have already been achieved, even ifthe
critical temperatures below which magnetic order is observed still are in the range
requiringliquid helium.
After two introductory chapters which explain the cooperative nature of
ferromagnetism and summarize the possible synthetic strategies to assemble magnetic
molecular materials, a first group of contributions outlines the synthetic strategies
developed so far using organic building blocks. The second block is more specifically
focused on approaches using organic radicals and metal ions, including also the
theoretical models which areneededinorderto develop parallel arrangements ofspins in
these materials. The third series of papers is mainly centered on specific physical
techniques of investigation of the magnetic materials. However, due to the
interdisciplinary approach which is needed in order to achieve some success with
magnetic molecular materials, all the contributions are generally a balanced mixture of
synthetic, theoretical, andphysicalaspects.
The reports on the discussions in the round tables conclude the volume. They
should be read with particular attention, because they summarize the results of many
excitingdiscussions whichoccurred during the pleasant stayin lin Ciocco".
It is certainly a pleasure to acknowledge the support of the Scientific Affair
Division of NATO which made the workshop possible; the University of Florence and
the Special Project on Advanced Materials of C.N.R. which generously cCHlponsorized
theevent.
Wedohopethat this bookwill represent astimulus for many more researchers to
step into this novel field. We look forward to the next meeting on magnetic molecular
materials to beheldinJapanin 1992.
Dante Gatteschi
Olivier Kahn
Joel S. Miller
Fernando Palacio
ix
Listo!Contributon
Pro!. Dante GaUeschi, Department of Chemistry, University of Florence, Via
Maragliano, 75/77, 50144- FLORENCE, Italy
Pro£. Klaus Becbgaard, The H. C. Oersted Institute, University of Copenhagen,
Universitetsparken5, 2100- COPENHAGEN, Denmark
Pro!. Marc DrilIon, E. H. I. C. S. - D. S. M., 1 rue Blaise Pascal, 67008
STRASBOURG,France
Pro£. Roland Georges, Laboratoirede Chimie du Solidedu C.N.R.S., Universitede
BordeauxI, 351 Cours delaLiberation, 33405- TALENCE Cedex, France
Pro!. Olivier Kahn, Institut de Chimie Moleculaire d'Orsay, Universite' de
Paris-Sud, Unite Associee420, 91405- ORSAYCedex, France
Dr. Christian Kollmar, Laboratoire de Spectroscopie des Elements de Transition,
Universite' de Paris Sud, Unite Associee420,91405- ORSAY Cedex, France
Pro!. Andre Rassat, Laboratoire de Chimie, Ecole Normale Superieure, 24, Rue
Lhomond, 75231- PARIS Cedex05, France
ReI,
Dr. Paul Departement de Recherche Fondamentale, CNRS, Centre d'Etudes
Nucleaires, 38041- GRENOBLE CEDEX, France
Dr. J. ,Schweizer, M. D. N. - D. R. F. - S. P. H., Centre d'Etudes Nucleaires,
38041 - GRENOBLECedex, France
Pro!. Michel Verdaguer, Laboratoire de Chimie des Metaux de Transition,
Universite' P. et M. Curie,4 PlaceJussieu, 75252- PARIS Cedex5, France
Pro£. WolfgangHaase, TechnischeHochschuleDarmstat, Institut fur Physikalische
Chemie, Petersenstrasse, 20, D-6100 DARMSTADT, Germany
Pro!. Cristiano Benelli, Department of Chemistry, University of Florence, Via
Maragliano, 75/77, 50144- FLORENCE, Italy
Prof. Koichi Itoh, Department of Chemistry, Osaka City University, Sugimoto,
Sumiyoshi-ku, 558, OSAKA,Japan
Pro!. Hiizu Iwaroma, Department of Chemistry, University of Tokyo, 7-3-1
Hongo, Bunkyo-Ku, 113, TOKYO, Japan
Prof. Minoru Kinoshita, Institute for Solid State Physics, The University of
Tokyo, Roppongi, Minato-ku, 106,TOKYO, Japan
Dr. A. J. van Duyneveldt, Kammerlingh Onnes Laboratory, Rijksuniversiteit Te
Leiden, Nieuwsteeg 18, LEIDEN, The Netherlands
Prof. Eugenio Coronado, Department de Quimica Inorganica, Universitad de
Valencia, Burjassot, VALENCIA, Spain
Pro!. Fernando Palacio, Instituto de Ciencia de Materiales de Aragon, CSIC<
Universidad de Zaragoza, 58009, ZARAGOZA, Spain
Dr. Jaime Veciana, Centro de Investigacion y Desarrollo - C. S. I. C., Jorge
GironaSalgado, 18-26,08034, BARCELONA, Spain
Prof. Hans U. Gudel, Institutefor Inorganicand Physical Chemistry, Universityof
Bern, Freierstrasse3, CH300- BERN 9, Switzerland
Prof. David Melville, Department of Physics and Astronomy, Lancashire
Polytechnic, PrestonPR1 2TQ, U. K.
Dr. D. A. Dixon, Central Research and Development, E.I. du Pont de Nemours &
Co., Inc., Experimental Station,WILMINGTON, DE 19880, U.S.A.
Prof. Dennis A. Dougherty, Department of Chemistry, California Institute of
Technology, PASADENA, CA 91125, U.S.A.
Pro£. Arthur J. Epstein, Department of Physics, Ohio State University, 174 W.
18thAvenue, COLUMBUS, OH43210, U.S.A.
Prof. David N. Hendrickson, Department ofChemistry, University ofCalifornia at
San Diego, LA JOLLA, CA 92093, U.S.A.
Prof. Timothy Hughbanks, Department of Chemistry, Texas A&M University,
COLLEGE STATION, TX77843, U.S.A.
Dr. Joel S. Miller, Central Research and Development Department, du Pont de
Nemours, Experimental Station, WILMINGTON, DE 19880, U.S.A.
xi