12
Organic and Inorganic Low-Dimensional Crystalline Materials
Organic and Inorganic Low-Dimensional Crystalline Materials
NATO ASI Series Advanced Science Institutes Series
A series presenting the results of activities sponsored by the NATO Science Committee, which aims at the dissemination of advanced scientific and technological knowledge, with a view to strengthening links between scientific communities.
The series is published by an international board of publishers in conjunction with the NATO Scientific Affairs Division
A Life Sciences B Physics
c Mathematical and Physical Sciences
D Behavioral and Social Sciences E Engineering and
Materials Sciences
F Computer and Systems Sciences G Ecological Sciences H Cell Biology
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Volume 168-0rganic and Inorganic Low-Dimensional Crystalline Materials edited by Pierre Delhaes and Marc Drillon
Series B: Physics
Organic and Inorganic Low-Dimensional Crystalline Materials Edited by
Pierre Delhaes CNRS, Paul Pasctll Center Unlvet11ity of Bordeau)( I Tatence, France
and
Marc Drillon EHICS Strasbourg, France
Springer Science+Business Media, LLC
Proceedings of a NATO Advanced Research Workshop on Organic and Inorganic Low-Dimensional Crystalline Materials, held May 3-8, 1987, in Minorca, Baleares, Spain
Library of Congress Cataloging in Publication Data
NATO Advanced Research Workshop on Organic and Inorganic Low-Dimensional Crystalline Materials (1987: Minorca, Spain)
Organic and inorganic low-dimensional crystalline materials I edited by Pierre Delhaes and Marc Drillon.
p. cm.-(NATO ASI series. Series B, Physics; v. 168) "Proceedings of a NATO Advanced Research Workshop on Organic and Inorganic
Low-Dimensional Crystalline Materials, held May 3-8, 1987, in Minorca, Baleares, Spain"-T.p. verso.
"Published In cooperation with NATO Scientific Affairs Division." Bibliography: p. Includes Index. ISBN 978-1-4899-2093-5 ISBN 978-1-4899-2091-1 (eBook) DOI 10.1007/978-1-4899-2091-1
1. Solid state physics-Congresses. 2. Solid state chemistry-Congresses. 3. Onedimensional conductors-Congresses. 4. Superconductors-Congresses. 5. Magnetic materials-Congresses. I. Delhaes, Pierre. I!. Orillon, Marc. Ill. North Atlantic Treaty Organization. Scientific Affairs Division. IV. Title. V. Series. QC176.A1N28 1987 530.4'1-dc19 87-28561
© Springer Science+Business Media New York 1987 Originally published by Plenum Press, New York in 1987 Softcover reprint of the hardcover 1st edition 1987
All rights reserved
No part of this book may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, microfUming, recording, or otherwise, without written permission from the Publisher
CIP
SPECIAL PROGRAM ON CONDENSED SYSTEMS OF LOW DIMENSIONALITY
This book contains the proceedings of a NATO Advanced Reserach Workshop held within the program of activities of the NATO Special Program on Condensed Systems of Low Dimensionality, running from 1983 to 1988 as part of the activities of the NATO Science Committee.
Other books previously published as a result of the activities of the Special Program are:
Volume 148 INTERCALATION IN LAYERED MATERIALS edited by M. S. Dresselhaus
Volume 152 OPTICAL PROPERTIES OF NARROW-GAP LOW-DIMENSIONAL STRUCTURES edited by C. M. Sotomayor Torres, J. C. Portal, J. C. Maan, and R. A. Stradling
Volume 163 THIN FILM GROWTH TECHNIQUES FOR LOW-DIMENSIONAL STRUCTURES edited by R. F. C. Farrow, S. S. P. Parkin, P. J. Dobson, J. H. Neave, and A. S. Arrott
PREFACE
The research of unitary concepts in solid state and molecular chemistry is of current interest
for both chemist and physicist communities. It is clear that due to their relative simplicity, low
dimensional materials have attracted most of the attention. Thus, many non-trivial problems were
solved in chain systems, giving some insight into the behavior of real systems which would
otherwise be untractable.
The NATO Advanced Research Workshop on "Organic and Inorganic Low-Dimensional
Crystalline Materials" was organized to review the most striking electronic properties exhibited by
organic and inorganic sytems whose space dimensionality ranges from zero (Od) to one (1d), and to
discuss related scientific and technological potentials. The initial objectives of this Workshop were,
respectively:
i) To research unitary concepts in solid state physics, in particular for one dimensional compounds,
ii) To reinforce, through a close coupling between theory and experiment, the interplay between
organic and inorganic chemistry, on the one hand, and solid state physics on the other,
iii) To get a salient understanding of new low-dimensional materials showing "exotic" physical
properties, in conjunction with structural features.
To reach these goals, the meeting was organized in three different steps as reported in the
table of contents. The first sessions were devoted to plenary lectures on the different classes of low
dimensional materials presenting either a mixed-valence or a magnetic character. Topics relative to
organic as well as inorganic materials were rewieved; this is rather unusual in standard conferences,
since researches on conducting and magnetic compounds are traditionally segregated. These
presentations were followed by a series of review papers on the physical properties, mainly on
magnetic aspects (phase transitions, linear and nonlinear excitations, Haldane conjecture, .. etc). One
special session was organized on the new superconducting materials, the organic ones as well as
the new ternary oxides which present superconductivity above the boiling point of liquid nitrogen. In
addition to the first series of review papers, several lectures were given on special topics in
connection with the main subject. These lectures were devoted to the problem of charge transfer in
biological systems, studies on large metallic clusters, which are regarded as "zero-dimensional
systems", and potential applications of mixed valence compounds, including equally organized
monomolecular layer systems (Langmuir-Blodgett films). The purpose of these special sessions was
both to increase the convergence between researches whose goals are different, and to get further
information before the round table discussions.
vii
For a complementary level of information, each participant presented one poster relevant to
these topics; the new results on magnetic chains as well as on conducting materials are included as
short contributions in this book.
The last part was devoted to the round tables on prospects and developments. The
proposed subjects (new conducting systems, new magnetic compounds, ferromagnets, competition
between magnetism - superconductivity and charge density waves, potential technology directions)
were presented by the group leaders, then discussed in small groups of abo!Jl ten persons.
Schemes for designing new types of materials were reported. Summaries of these discussions are
given in the last part of this volume.
The concluding remart<s .were given by Prof. V.J. Emery, who emphasized the interest in
using large equipments, such as different neutron reactors or synchrotron sources, for analyzing
crystal structures (long-range order but also local organization, structural phase transitions, .. etc). An
outstanding example of new unexpected and very stimulating findings is the discovery of the new
"high T c" superconductors.
We wish to mention that this NATO wort<shop was prepared and organized thanks to the
positive contribution of the organizing committee (D. Beltran (Spain), R. Cariin (USA), LJ. de Jongh
(Netheriands), and J. Rouxel (France)), and the enthusiasm during the preparation of study-group
reports of the leaders (A. Barraud (France), D. Brom (Netheriands), R. Cariin (USA), H.J. Keller
(Germany) and F. Palacio (Spain)).
Finally, we wish to thank the panel on "Condensed Systems of Low Dimensionality" of
NATO's Scientific Affairs Division for the financial and administrative support which made this
workshop possible.
P. Delhaes and M. Drillon
viii
CONTENTS
PLENARY LECTURES
SOLID STATE CRYSTAL CHEMISTRY OF lD INORGANIC CHAINS J. Rouxel
STRUCTURES AND PROPERTIES OF LOW-DIMENSIONAL METAL COMPLEXES A.E. Underhill
1
17
LIGAND BRIDGED MIXED-VALENCY METAL CHAIN COMPLEXES: PROTOTYPE N-SITE, N-ELECTRON SYSTEMS WITH ELECTRON-PHONON COUPLING • • • • • • • • • • • 33
P. Day
ELECTRONIC STRUCTURE OF LINEAR CHARGE TRANSFER SOLIDS Z.G. Soos
47
INSULATING MAGNETIC CHAINS: IONOCOVALENT COMPOUNDS • • • • • • • . • 63 M. Steiner
INSULATING MAGNETIC CHAINS: RECENT MODELS AND MATERIALS C.P. Landee
'15
MAGNETIC ORDERING OF MnJI cull BIMETALLIC SYSTEMS,~ DESIGN OF MOLECULAR FERROMAGNETS • . • • • • • • • • • • • • • • • • • • • • • • • • • • • 93
o. Kahn
EXOTIC MAGNETIC SYSTEMS • . • • • • . • • • • • • • • c. Benelli, A. Caneschi, D. Gatteschi, P. Rey.
109
MAGNETIC PHASE TRANSITIONS IN LOW DIMENSIONAL SYSTEMS • • • • • • • • 125 J.P. Renard
CHAIN-,LIKE MAGNETIC SYSTEMS: NON LINEAR EXCITATIONS AND QUANTUM EFFECTS • • • • • • • . • • • • • • • • • • • • • • . . • 141
K. Kopinga, W.J.M. de Jonge
FERROMAGNETIC EXCHANGE IN MOLECULAR SOLIDS J.S. Miller, A.J. Epstein
THEORY OF THE ONE AND TWO DIMENSIONAL ELECTRON GAS v. J. Emery
ANION PERIODICITY AND ORDERING EFFECTS IN ONE DIMENSIONAL ORGANIC
159
•. 175
CONDUCTORS • • • • • • • • • • • • • • • • • • • • • • • • . . • • • . 185 J.P. Pouget
ix
MAGNETIC PROPERTIES OF BECHGAARD SALTS AND RELATED COMPOUNDS, ROLE OF THE ELECTRONIC LOCALIZATION • • • • • • • • • • • • . • • • • 201
c. Coulon
MOLECULAR METALS AND SUPERCONDUCTORS: BEDT-TTF RADICAL SALTS • • • • • 219 D. Schweitzer, H.J. Keller
POLYNUCLEAR KETAL CLUSTER COMPOUNDS: A NEW CHEMICAL SUBMICRON STRUCTURE • • • • • • • • • . • • • • • • • 231
L.J. de Jongh
KETAL CLUSTERS ACTIVE SITES IN PROTEINES • • • • • • • • • • • • • • • 243
E.I. Solomon, J.E. Pates, T.D. Westmoreland Lung-Shan Kan, M.D. Allendorf, D.J. Spira-Solomon
LANGMUIR-BLODGETT FILMS OF DONOR-SIGMA-ACCEPTOR MOLECULES AND PROSPECTS FOR ORGANIC RECTIFIERS • • • • • • • • • • . • • • • . • . • . 271
R.K. Metzger, C.A. Panetta
MIXED VALENCE COMPOUNDS: POTENTIAL APPLICATIONS IN MATERIALS AND MOLECULAR ELECTRONICS • • • • • . • • • • • . • . . • • • . . . • 287
J.P. Launay
COMMUNICATIONS ON MOLECULAR CONDUCTORS
DIMETHYL-DICYANOBENZOCHINODIIKINE WITH Li+, Ag+ AND cu+ AS COUNTERIONS: NEW RADICAL-ANION SALTS WITH EXTREMELY HIGH CONDUCTIVITY . • . • 297
J.V. von Schultz, M. Bair, H.P. Werner, A. Aumuller, P. Erk, s. Hunig
CONDUCTIVE SOLIDS BASED ON SOME NEW MOLECULES WITH ISOTHIAZOLO-RINGS • • • • • • • • • . • • • 301
G. Papavassiliou, G.A. Kousdis, V. Gionis, J.S. Zambounis, · S.Y. Yiannopoulos
PYRIDINO-TETRAHETEROFULVALENES AND A FEW OF THEIR SALTS • • . . . . • 305 G. Papavassiliou, S.Y. Yiannopoulos, J.S. Zambounis
SYSTEMATIC VARIATIONS OF THE BEDT-TTF RING SYSTEMS: SYNTHESIS AND PHYSICAL PROPERTIES OF NEW RADICAL! CATION SALTS
R.R. Schumaker, E. Dupart, R. Laversanne, C. Coulon, P. Delhaes
TRANSFER INTEGRALS IN (DIMET) 2 MF6 : COMPARISON OF EHT AND CNDO
• 309
CALCULATIONS • • • • • • • • . . • • • • • • . . . • . 313 L. Ducasse, H. Abderrabba, A. Fritsch, B. Gallois
CRYSTAL STRUCTURE AND PHYSICAL PROPERTIES OF A NEW CONDUCTING CHARGE TRANSFER SALT: (BEDT-TTF) 3 Cl2 • 2H2 0 . • . • • • • 317
D. Chasseau, D. Watkin, K. Rosseinsky, K. Kurmoo, P. Day
ELECTRONIC EXCITATIONS IN (BEDT-TTF) SALTS H.W. Helberg
• • • • • 321
EXISTENCE OF TWO PHASES IN ~-(BEDT-TTF) 2 I3 : PROOF BY RESONANCE RAMAN SPECTROSCOPY . • • • • • • • • • • • • • • • • • . . • • • • • . . • • 325
R. Swietlik, D. Schweitzer, H.J. Keller
X
RESONANCE RAMAN SPECTRA OF I; IN TEDA(TRIETHYLENEDIAMINE) I TCNQ 2' ~
AND ~-(BEDT"'-TTF) 2 I3 ••••••••••••• • 329 A.D. Bandrauk, K.D. Truong, c. Carlone
IMPORTANCE OF INTERMOLECULAR HYDROGEN-) HYDROGEN AND HYDROGEN- ANION CONTACTS FOR THE LATTICE SOFTNESS AND THE SUPERCONDUCTIVITY OF ~-(ET) 2 X <x- = I; , Aui; , IBr; l . . . . . . . . . . . . . . . . . . . . . 333
M.H. Whangbo, J.M. Williams, A.J. Schultz, A. Beno
SYNTHESIS AND CHARACTERIZATION OF TTF SALTS OF PLANAR PLATINIUM, PALLADIUM', NICKEL AND COPPER (1,2, DITHIO-OXALATO S,1S') ANIONS AND THE CRYSTAL AND MOLECULAR STRUCTURE OF BIS(TETRATHIAFULVALENENIUM) BIS(1,2, DITHIOOXALATO S,S') PALLADATE (ll) • • • • • • • • • • • • • • • • • 337
C. Bellito, M. Bonamico, V. Fares, P. Imperatori, s. Patrizio
FINE STRUCTURE TO THE v AND 2v BANDS (v = v(Cl.PtTil -Cl) THE SYMMET~IC 1 1 1
CHAIN STRECHING MODE) OF [Pt (en) 2 ] [Pt (en) 2 Cl 2 ] [Cl04 ] 4 • • • • • • • 341 R.J.H. Clark, V.B. Croud
CORRELATION OF SPECTROSCOPIC AND MAGNETIC DATA OF TWO CHARGE TRANSFER COMPOUNDS OF TCNQ WITH CATIONIC COPPER CHELATES . • • . • • • • • • • 345
M. Schwartz, W.E Hatfield
COUNTER-ION INFLUENCES ON THE ELECTRICAL CONDUCTION PROPERTIES OF 1,2,-DITHIOLENE COORDINATION COMPOUNDS • • • • • • • • • • • 349
L.R. Groenevel, G.J. Kramer, T.B.L.W. von Marinelli, H.B. Brom, J.G. Haasnoot, J. Reedijk
SINGLE CRYSTAL ESR STUDIES OF N-TETRABUTYLAMMONIUM' NICKEL' (0-BENZENE-DISELENOLATE); AND RELATED TRANSITION METAL COMPLEXES 353
M.T. Jones, J.H. Roble, M. Sing, T. Marvo
ESR OF SOME M[Pt(mnt) 2 ] AND M[Pd(mnt) 2 ] POLYCRYSTALLINE COMPLEXES •• 357 M.T. Jones, J.M. Patane, P.I. Clemenson, A.E. Underhill
A NEW FAMILY OF ONE-DIMENSIONAL CONDUCTORS DERIVED FROM MAGNUS GREEN-TYPE SALTS [Pt(NH3 ) 4 ] [PtX4 ] (X= Cl,Br): CLASS TI AND I MIXED-VALENCE CHAINS IN A DOUBLE CHAIN STRUCTURE • • • • • • . • • • • . • • . • • • . • • . . 361
J.P. Catinat, T. Robert, G. Offergeld
CONDUCTIVE MATERIALS BASED ON RHODIUM AND IRIDIUM COMPLEXES OF CARBOXYAZOLES • • . • • • • • • . • • • • • • • • • • • • • 365
J.C. Bayon, G. Net
ONE DIMENSIONAL ELECTRONIC SYSTEMS: METALLIC AND SYNTHETIC WIRES • • • 369 H.B. Brom, G.J. Kramer
SUPERCONDUCTIVITY IN RAPIDLY COOLED Gd3 Ba3 Cu4 02 • • • • • • • • • • 373 D.A. Robinson, A. Morrobel-Sosa, c. Alexander, J.S. Thrasher, c. Asavaroengchai, R.M. Metzger
COMMUNICATIONS ON MAGNETIC CHAINS
DIMENSIONAL CROSSOVER IN THE MOLECULAR FERROMAGNETS DECAMETHYLFERROCENIUM TETRACYANOETHENIDE • • • • • • • • • • • . 377
S. Chittipeddi, A.J. Epstein, J.S. Miller
xi
SYNTHETIC PATHWAYS TO LOW DIMENSIONAL COMPOUNDS CONTAINING TRANSITION KETAL IONS .AND NITROXIDE RADICALS . • • • • • • • • • • •
A. Canneschi, D. Gatteschi, J. Laugier, P. Rey, R. Sessoli, c. Zanchini
381
MAGNETIC PROPERTIES OF COUPLED LANTHANIDE-RADICAL SPECIES •••• 385 c. Benelli, A. Caneschi, D. Gatteschi, J. Laugier, P. Rey
MAGNETIC BEHAVIOR OF lD HELICOIDAL CHAINS IN BA7 CuFe6 F34
A NEW KIND OF FERRIMAGNETIC ld SYSTEM • • ••• 389 J. Renaudin, G. Ferey, K. Zemirli, F. Varret, A. de Kozak, K. Drillon
MAGNETIC ANISOTROPY STUDIES OF ld BIMETALLIC FERRIKAGNETIC COMPOUNDS . . . • • • . . • • . . •... 393
Yu Pei, K. Verdaguier, 0. Kahn, J.P. Renard, J. Sletten
CRYSTAL CHEMISTRY AND MAGNETIC PROPERTIES OF NEW FLUORIDES WITH USOVITE-TYPE STRUCTURES • 397
J. Darriet, Xu Qiang, A. Tressaud, R. Georges, J.L. Soubeyroux
DESIGN OF LOW DIMENSIONAL FERRIMAGNETIC COMPOUNDS: NEW MAGNETIC LATTICES IN THE "EDTA-FAKILY" •••• 401
E. Coronado, A. Barba, D. Beltran, R. Burriel, R. Carlin
LOW TEMPERATURE INVESTIGATION OF THE THERMAL AND MAGNETIC PROPERTIES OF ld FERRIMAGNETIC SYSTEMS • • • • • • • • • • • • • • • • • • • 405
E. Coronado, P.R. Nugteren, K. Drillon, D. Beltran, L.J. de Jongh, R. Georges
FERRIKAGNETISM IN HOKOKETALLIC LINEAR CHAINS: CuX2 .4/3TKSO, X = Cl, Br • • • • • • • • • • • • • • • • • • . • • • • • • 409
C.P. Landee, A. Djili, K. Newhall, D.E. Mudgett, R.D. Willett, H. Place, B. Scott
MAGNETISM OF QUANTUM-CLASSICAL FERRIMAGNETIC CHAINS SHOWING ALTERNATE HEISENBERG COUPLING: APPLICATION TO MnCu (obp) (H2 0) 3 , H2 0 413
J. Curely, R. Georges, J.C. Gianduzzo, Q. Xu, 0. Kahn, Y. Pei, J. Sletten
DIMERS, REGULAR AND DOUBLE CHAINS IN VANADYL (IV) PHOSPHATES •••.• 417 G. Villleneuve, P. Amoros, D. Beltran, M. Drillon
NEW ld-SYSTEMS MADE OF INTERACTING COPPER(II) TRIMERS; EXPERIMENTAL AND THEORETICAL INVESTIGATION • • • • • •
M. Drillon, M. Belaiche, J.M. Heintz, G. Villeneuve, A. Boukhari, J. Aride
421
MAGNETIC BEHAVIOR OF HYDRATED TETRAFLUOROMANGANATES(III) ••••••• 425 F. Palacio, M. Andres
STRUCTURE AND MAGNETISM IN LINEAR CHAIN FLUOROMANGANATES(III) W. Massa, J. Pebler, F. Hahn, D. Babel
MAGNETO-STRUCTURAL CORRELATIONS IN ~-HALO BRIDGED
429
COPPER(II) CHAINS • • • • • • • • • • • • • • ••••••• 433 D. Beltran, J.V. Folgado, R. Iba~ez, E. Coronado, J.L. Mesa, T. Rojo, G. Villeneuve
xii
CLUSTER CALCULATIONS ON THE CHAIN COMPOUND AQUA[N-(SALICYLADIMINATO)GLYCINATO]COPPER(II) HEMIHYDRATE • • • • • • 437
i.E. Hatfield, J.H. Helms, B.R. Rohrs
NON-LINEAR EXCITATIONS IN THE ANTIFERROMAGNETIC CHAIN OF Rb2 Mn1 _xFexF8 *H2 0 (X,0.50) • • • • • • • • • • • • • • • . . • • 441
J. Pebler, D. Babel
ONE DIMENSIONAL EXCITATION ENERGY TRANSFER IN TMMC AND RELATED COMPOUNDS • • • • • • • • • • • • • • • • . • • • • • • . 445
R. Knochenmuss, H.U. Gudel
QUANTUM ENERGY GAP IN THE S=l HEISENBERG ANTIFERROMAGNET NENP: EXPERIMENTAL DATA AND HALDANE CONJECTURE • • • • • • • • • • •
J.P. Renard, K. Verdaguer, L.P. Regnault, W.A.C. Erkelens, J. Rossat-Mignod, W.G. Stirling
• • • 448
NEUTRON DIFFRACTION STUDY OF KnRhAs NEAR TN: THE CRITICAL REGIME 453 J. Bartolome, B. Chenevier, K. Bacman, D. Fruchart, c. Rillo, R. Navarro, J.P. Regnault, P. Erkelens, J. Rossat-Mignod, R. Fruchar
REPORTS ON ROUND TABLES
NEW HIGHLY CONDUCTING SYSTEMS • • • • • • . . • • • • • • • • • • • 457 K.J. Keller, A.D. Bandrauk, J.C. Bayon, C. Bellito, R.J.M. Clark P. Day, J.G, Haasnoot, i.E. Hatfied, M.T. Jones, G. Papavassiliou T. Robert, J.U. von Schultz, A.E. Underhill, K.M. Whangbo
FERROMAGNETIC COMPOUNDS • • 463 R.L. Carlin, D. Beltran, R. Burriel, C. Benelli, A. Caneschi, o. Kahn, C.P. Landee, J. Pebler
ROUND TABLE ON NEW LOW-DIMENSIONAL MAGNETIC MATERIALS • • . • • • • • 465 F. Palacio, E. Coronado, J. Darriet, K. Drillon, G. Ferey, D. Gatteschi, W. Kassa, P. Rey, T. Rojo, z. Soos, J. Torrance, M. Verdaguer, G. Villeneuve
ROUND TABLE 4. COMPETITION BITVEIK (SUPER)CONDUCTIVITY, CDW/SDW, (SPIN)PEIERLS.TRANSITIOIS AND MAGNETISM ••••••••••••••• 471
H.B. Brom, D. Chasseau, C. Coulon, L. Ducasse, V.J. Emery, H.W. Helberg, J.P. Pouget, D.J.K. Schweitzer, M. Steiner, M. Weger
ROUND TABLE ON POTENTIAL TECHNOLOGICAL APPLICATIONS A. Barraud, P. Delhaes, L.J. De Jongb, H. Gudel, 0. Kahn, J.P. Launay, R. Metzger, J.S. Killer, J.P. Renard
PARTICIPANTS • • • • • • • • • • • • • • • • • • • •
INDEX • • • • • • • • • • • • • • • • • • • • • • •
475
479
481
xiii
