Table Of ContentApplications of Organometallic Chemistry in the
Preparation and Processing of Advanced Materials
NATO ASI Series
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Series E: Applied Sciences -Vol. 297
Applications of
Organometallic Chemistry in the
Preparation and Processing of
Advanced Materials
edited by
John F. Harrod
Department of Chemistry,
McGiII University,
Montreal, Quebec, Canada
and
Richard M. Laine
Materials Science & Engineering,
College of Engineering,
Ann Arbor, Michigan, U.S.A.
Springer Science+Business Media, B.V.
Proceedings of the NATO Advanced Research Workshop on
Applications of Organometallic Chemistry in the
Preparation and Processing of Advanced Materials
Cap D'Agde, France
September 4-9, 1994
A C.I.P. Catalogue record for this book is available from the Library of Congress.
ISBN 978-94-010-4149-2 ISBN 978-94-011-0337-4 (eBook)
DOI 10.1007/978-94-011-0337-4
Printed an acid-free paper
AII Rights Reserved
© 1995 Springer Science+Business Media Dordrecht
Originally published by Kluwer Academic Publishers in 1995
Softcover reprint of the hardcover 1 st edition 1995
No part of the material protected by this copyright notice may be reproduced or
utilized in any form or by any means, electronic or mechanical, includ ing photo
copying, recording or by any information storage and retrieval system, without written
permission from the copyright owner.
TABLE OF CONTENTS
Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. vii
List of Participants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ix
List of Contributing Authors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xi
Metal Oxide Materials -
Synthesis, Processing, Characterization
Sol-Gel Approaches to Advanced Materials
J. Livage ..................................................... 3
Sol-Gel Methods for the Production of Novel Catalytic Materials -
Amorphous, Microporous Metal Oxides
W.F. Maier, F.M. Bohnen, J. Heilmann, S. Klein, H.-c. Ko, M.F. Mark,
S. Thorimbert, l.-c. Tilgner and M. Wiedorn . . . . . . . . . . . . . . . . . . . . . . . . . .. 27
Chemical Routes to Nanostructured Ceramics and Composites
H.K. Schmidt ................................................. 47
Chemicals, Polymers and Ceramics from the Beach. II.
R.M. Laine .................................................. 69
Use of Organometallics and Metal Carbonyls for Intrazeolite Cluster Formation
S. Ozkar .................................................... 79
Nonoxide Materials -
Synthesis, Processing, and Characterization
NMR Characterization of Ceramic Materials Derived from Preceramic Polymers
F. Babonneau ................................................ 103
Poly(methylsilane) and Poly(Hydrazinomethylsilane) as Precursors for Silicon
Containing Ceramics
M. Scarlete, J. He, J.F. Harrod and I.S. Butler ......................... 125
SiC and SiCN-Based Materials: The Model and Copolymer Ways for a Rational
Approach to Their Precursors
M. Biro!, J.-P. Pillot and J. Dunogues ............................... 141
Non-Oxide Silicon-Based Ceramics form Novel Silicon Polymers
R. Riedel, A. Kienzle and M. FriefJ ................................. 155
vi
Hydridopolycarbosilane Precursors to Silicon Carbide. Synthesis, Pyrolysis and
Applications as a SiC Matrix Source
L. V. Interrante, C. W. Whitmarsh, W. Sherwood, H.-J. Wu, R. Lewis and
G. Maciel ................................................... 173
Ceramics from Molecular Precursors. Transition Metal Activation of Silicon
Carbide Precursors
R.J.P. Corriu, M. Enders, S. Huille, L. Lutsen and J.J.E. Moreau ............ 185
Novel Materials with Novel Properties
Organosilicon Polymers with Bis-Acetylenic Units: Conductivity and Ceramisation
Studies
R. Corriu, P. Gerbier, G. Guerin and B. Henner ........................ 203
Molecular Assembly and Molecular Recognition. Organometallic and Sol-Gel
Materials for Chemical Sensing
J.D. Wright and R.J.M. Nolte ..................................... 223
The Molecular Tinkertoy Approach to Materials. Towards a Molecular-Size Civil
Engineering Construction Kit
J. Michl .................................................... 243
Met-Cars: A New Family of Metal-Carbon Clusters
A. W. Castleman, Jr . ............................................ 269
Construction of Ordered Solids and Polymers from Fullerene Components
A.L. Balch ................................................... 283
Synthesis and Solid State Properties of Poly-, Oligo- and Multidecker
Metallocenes
D. O'Hare, S. Barlow, A.K. Hughes, I. Manners, c.B. Honeyman, J.K. Pudelski
and A.J. Lough ............................................... 303
Chemical Approaches to Nanoscale Magnetic Materials
D. Gatteschi ................................................. 317
Well-Defined Conjugated Rigid-Rods as Multifunctional Materials: Linear and
Nonlinear Optical Properties and Liquid Crystalline Behavior
P. Nguyen, G. Lesley, C. Dai, N.J. Taylor, T.B. Marder, V. Chu, C. Viney,
I. Ledoux and J. Zyss ........................................... 333
Author Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 349
Subject Index ................................................ 351
PREFACE
This volume is the fourth in a series of books concerned with the materials' chem
istry of inorganic and organometallic polymers (lOPs). The common thread which
links most of the subjects treated in the present and earlier volumes is the synthesis
and processing of molecular, inorganic objects which are packaged in an organic shell.
This organic shell confers the properties prerequisite to easy processing under mild
conditions and its removal generates the core as a pristine inorganic material. As a
result of the mild conditions of the transformation reactions, the inorganic products are
usually obtained as amorphous solids which present considerable challenge with
respect to detailed structural analysis. For this reason, the rate of evolution of the field
has been, to a large degree, tied to the evolution of the analytical methods available for
structural analysis of such materials.
In the ten years since the scientific rationale for the design, synthesis, and applica
tion of lOPs was first conceptualized, we have witnessed the first tentative exploration
of lOPs as precursors to new materials (Transformation of Organometallics into Com
mon and Exotic Materials: Design and Activation, NATO ASI Series Vol 141, 1987),
with efforts focusing on the design and synthesis of novel ceramic precursors. As
expertise developed, the next level of effort combined precursor synthesis studies with
efforts to characterize the transformation processes that occur as lOPs are converted to
ceramic materials. Coincidentally, efforts were made to examine the intrinsic proper
ties of lOPs to firmly establish their relevance to Chemistry and Materials Science
(Inorganic and Organometallic Oligomers and Polymers, J.P. Harrod and R.M. Laine,
eds., 1991, Kluwer Publishers. Inorganic and Organometallic Polymers with
Special Properties, NATO ASI Series Vol. 206, 1992).
This volume witnesses the maturation of the polymer precursor approach to materi
als synthesis with examples of processing ceramic shapes for mechanical properties
applications, the development of sophisticated, noninvasive analytical techniques, and
ofIOP design rationales that rely on (now) well-defined processing-property relation
ships. Included in the latter are methodologies for producing multifunctional lOPs
that provide ion conductivity, gas sensing capabilities, bioactivity, magnetic proper
ties, etc. combined with processability.
Rather than the maturation process leading to closure, new chemistries, analytical
tools, and performance demands have spawned yet more new opportunities for lOPs in
materials science. The existence of well-defined lOPs, and the exquisite control that
can be exerted on sol-gel systems, now provide access to such a variety of mixed
organic-organometallic and/or inorganic hybrid systems that their exploitation is
likely to develop into an entirely new field of materials' chemistry. On the other hand,
the advent of "bucky balls", Met-Cars, dopable preceramics, rigid-rod organometallics,
and, "molecular tinkertoys" provide exciting future avenues of research whose out
comes are difficult to predict.
We would like to thank NATO and the U.S. Office of Naval Research, European
Office, for generous support of this meeting. In particular, we would like to thank the
organizing committee and especially Professor R.J.P. Corriu for help with the onsite
preparations.
John P. Harrod Richard M. Laine
co-editor co-editor
VII
LIST OF PARTICIPANTS
~ Affiliation
Babonneau, F. Chimie de la Matiere Condensee, Universite Pierre et
Marie Curie, Paris, France
Balch, A. Dept. of Chemistry, University of California, Davis,
Davis, CA
Birot, M. Laboratoire de Chimie Organique et Organometallique,
Universite Bordeaux, Bordeaux, France
Castleman, A.W. Dept. of Chemistry, Penn. State University, University
Park, PA
Corriu, R.I.P. Dept. de Chime Organique Fine, Universite de
Montpellier II, Montpellier, France
Gatteschi, D. Dept. of Chemistry, University of Florence, Florence,
Italy
Guerin, C. Dept. de Chime Organique Fine, Universite de
Montpellier II, Montpellier, France
Harrod, J.F. Chemistry Dept., McGill University, Montreal, Canada
Interrante, L.V. Dept. of Chemistry, Rensselaer Polytechnic Institute,
Troy, N.Y.
Laine, R. M. Dept. of Materials Sci. and Eng., University of
Michigan, Michigan
Maier, W.F. Max-Planck-Institut ftir Kohlenforshung, Miilheim an
der Ruhr, Germany
Marder, T.B. Dept. of Chemistry, University of Waterloo, Ontario,
Canada
Michl, J. Dept. of Chemistry and Biochemistry, University of
Colorado, Boulder, CO
Moreau, J.J.E. Laboratoire de Chimie Organometallique, Ecole
Nationale Su¢riure de Chimie, Montpellier, France
O'Hare,D. Inorganic Chemistry Laboratory, Oxford, U.K.
Ozkar, S. Dept. of Chemistry, Middle East Technical University,
Ankara, Turkey
Riedel, R. Technische Hochschule Darmstadt, Darmstadt, Germany
Schmidt, H.K. Institut fUr Neue Materialien, Saarbriicken, Germany
Wright, J.D. Centre for Materials Research, University of Kent,
Canterbury, U.K.
IX
x
Ko. H-C. Max-Planck-Institut flir Kohlenforshung, Miilheim an
der Ruhr, Germany
Laine, R.M. Dept. of Mater. Sci. and Eng., University of Michigan,
Michigan
Ledoux, I. CNET, France Telecom, Laboratoire de Bagneux,
Bagneux, France
Lesley, G. Dept. of Chemistry, University of Waterloo, Ontario,
Canada
Lewis, R. Dept. of Chemistry, Colorado State University, Fort
Collins, CO
Livage, J. Chimie de la Matiere Condensee, Universite Pierre et
Marie Curie, Paris, France
Lough, AJ. Dept. of Chemistry, University of Toronto, Toronto,
Canada
Lutsen, Laurence Dept. de Chime Organique Fine, Universite de
Montpellier II, Montpellier, France
Maciel, G. Dept. of Chemistry, Colorado State University, Fort
Collins, CO
Maier, W.F. Max-Planck-Institut ftir Kohlenforshung, Miilheim an
der Ruhr, Germany
Marder, T.B. Dept. of Chemistry, University of Waterloo, Ontario,
Canada
Mark, M.F. Max-Planck-Institut flir Kohlenforshung, Miilheim an
der Ruhr, Germany
Manners, 1. Dept. of Chemistry, University of Toronto, Toronto,
Canada
Michl, J. Dept. of Chemistry and Biochemistry, University of
Colorado, Boulder, CO
Moreau, J.J.E. Laboratoire de Chimie Organometallique, Ecole
Nationale SupcSriure de Chimie, Montpellier, France
Nolte, R.J.M. Dept. of Organic Chemistry, University of Nijmegen,
Nijmegen, The Netherlands
Nguyen, P. Dept. of Chemistry, University of Waterloo, Ontario,
Canada
O'Hare,D. Inorganic Chemistry Laboratory, Oxford, U.K.
Ozkar, S. Dept. of Chemistry, Middle East Technical University,
Ankara, Turkey
Pillot, J.-P. Laboratoire de Chimie Organique et Organometallique,
Universite Bordeaux, Bordeaux, France
Pudelski, J.K. Dept. of Chemistry, University of Toronto, Toronto,
Canada
Riedel, R. Technische Hochschule Darmstadt, Darmstadt, Germany
Scarlete, M. Chemistry Dept., McGill University, Montreal, Canada
Schmidt, H.K. Institut ftir Neue Materialien, Saarbrticken, Germany
Sherwood, W. Starfire Systems, Glenville, NY
LIST OF CONTRIBUTING AUTHORS
Nrulli< Affiliation
Babonneau, F. Chimie de la Matiere Condensee, Universite Pierre et
Marie Curie, Paris, France
Balch, A. Dept. of Chemistry, University of California, Davis,
Davis, CA
Barlow, S. Inorganic Chemistry Laboratory, Oxford, U.K.
Bohnen, F.M. Max-Planck-Institut ftir Kohlenforshung, Miilheim an
der Ruhr, Germany
Birot, M. Laboratoire de Chimie Organique et Organometallique,
Universite Bordeaux, Bordeaux, France
Butler, I.S. Chemistry Dept., McGill University, Montreal, Canada
Castleman, A.W. Dept. of Chemistry, Penn. State University,
University Park, PA
Chaoyang, D. Dept. of Chemistry, University of Waterloo, Ontario,
Canada
Chu, V. Molecular Bioengineering Program, University of
Washington, Seattle, WA
Corriu, RJ.P. Dept. de Chime Organique Fine, Universite de
Montpellier II, MontpelIier, France
Dunogues, J. Laboratoire de Chimie Organique et Organometallique,
Universite Bordeaux, Bordeaux, France
Enders, M. Dept. de Chime Organique Fine, Universite de
Montpellier II, Montpellier, France
Friess, M. Technische Hochschule Darmstadt, Darmstadt, Germany
Gatteschi, D. Dept. of Chemistry, University of Florence, Florence,
Italy
Gerbier, P. Laboratoire de Chimie Organometallique, Universite de
Montpellier, Montpellier, France
Guerin, C. Laboratoire de Chimie Organometallique, Universite de
Montpellier, Montpellier, France
Harrod, J.F. Chemistry Dept., McGill University, Montreal, Canada
He, J. Chemistry Dept., McGill University, Montreal, Canada
Heilmann, J. Max-Planck-Institut flir Kohlenforshung, Miilheim an
der RUhr' Germany
Henner, B. Laboratoire de Chimie Organometallique, Universite de
Montpellier, Montpellier, France
Honeyman, C.H. Dept. of Chemistry, University of Toronto, Toronto,
Canada
Hughes, A.K. Inorganic Chemistry Laboratory, Oxford, U.K.
Huille, S. Dept. de Chime Organique Fine, Universite de
Montpellier II, Montpellier, France
Interrante, L.V. Dept. of Chemistry, Rensselaer Polytechnic Institute,
Troy, N.Y.
Kienzle, A. Technische Hochschule Darmstadt, Darmstadt, Germany
Klein, S. Max-Planck-Institut flir Kohlenforshung, Miilheim an
der Ruhr, Germany
xi
