Molecular Engineering for Advanced Materials › content › pdf › bfm%3A978-94... ·...

Molecular Engineering for Advanced 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 Behavioural and Social Sciences E Applied Sciences

F Computer and Systems Sciences G Ecological Sciences H Cell Biology I Global Environmental Change

PARTNERSHIP SUB-SERIES

1. Disarmament Technologies 2. Environment 3. High Technology 4. Science and Technology Policy 5. Computer Networking

Plenum Publishing Corporation London and New York

Kluwer Academic Publishers Dordrecht, Boston and London

Springer-Verlag Berlin, Heidelberg, New York, London, Paris and Tokyo

Kluwer Academic Publishers Springer-Verlag Kluwer Academic Publishers Kluwer Academic Publishers Kluwer Academic Publishers

The Partnership Sub-Series incorporates activities undertaken in collaboration with NATO's Cooperation Partners, the countries of the CIS and Central and Eastern Europe, in Priority Areas of concern to those countries.

NATO-PCO-DATA BASE

The electronic index to the NATO ASI Series provides full bibliographical references (with keywords and/or abstracts) to more than 30000 contributions from international scientists published in all sections of the NATO ASI Series. Access to the NATO-PCO-DATA BASE is possible in two ways:

- via online FILE 128 (NATO-PCO-DATA BASE) hosted by ESRIN, Via Galilee Galilei, 1-00044 Frascati, Italy.

- via CD-ROM "NATO-PCO-DATA BASE" with user-friendly retrieval software in English, French and German(© WTV GmbH and DATAWARE Technologies Inc. 1989).

The CD-ROM can be ordered through any member of the Board of Publishers or through NATO­PCO, Overijse, Belgium.

Series C: Mathematical and Physical Sciences- Vol. 456

Molecular Engineering for Advanced Materials

edited by

Jan Becher Department of Chemistry, University of Odense, Odense, Denmark

and

Kjeld Schaumburg CISMI, Department of Chemistry, University of Copenhagen, Copenhagen,Denma~

Springer-Science+Business Media, B.V.

Proceedings of the NATO Advanced Research Workshop on Molecular Engineering for Advanced Materials Hindsgavl, Denmark May7-11,1994

A C.I.P. Catalogue record for this book is available from the Library of Congress.

ISBN 978-90-481-4521-8 ISBN 978-94-015-8575-0 (eBook) DOI 10.1007/978-94-015-8575-0

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, including photo­copying, recording or by any information storage and retrieval system, without written permission from the copyright owner.

This book contains the proceedings of a NATO Advanced Research Workshop held within the programme of activities of the NATO Special Programme on Supramolecular Chemistry as part of the activities of the NATO Science Committee.

Other books previously published as a result of the activities of the Special Programme are:

WIPFF, G. (Ed.), Computational Approaches in Supramolecular Chemistry. (ASIC 426) 1994. ISBN 0-7923-2767-5

FLEISCHAKER, G.R., COLONNA, S. and LUISI, PL. (Eds.), Self-Production of Supramolecular Structures. From Synthetic Structures to Models of Minimal Living Systems. (ASIC 446) 1994. ISBN 0-7923-3163-X

FABBRIZZI, L., POGGI, A. (Eds.), Transition Metals in Supramolecular Chemistry. (ASIC 448) 1994. ISBN 0-7923-3196-6

CONTENTS

Participants

Introduction

The Self-Assembly of Redox-Active and Photo-Active Catenanes and Rotaxanes

Jon A. Preece, J. Fraser Stoddart

Advantages of the Rotaxane Framework for the Construction of Switchable Molecular Devices

Richard A. Bissell, Emilio Cordova, J. Fraser Stoddart, and Angel E. Kaifer

The Polyrotaxane Architecture. A New Approach to Molecular Engineering

Harry W. Gibson, Shu Liu, Ya Xi Shen, Mukesh Bheda, Sang-hun Lee and Feng Wang

"Smart" Cascade Macromolecules G.R. Newcome and G.R. Baker

Tailoring Cyclodextrins for the Construction of Large Scale Scale Molecular Assemblies

A.W. Coleman, M. Munoz, M. Eddaoudi, H. Parrot-Lopez, P. Prognon, J-M. Valleton, A. Baszkin, S. Alexandre, F. Sommer, T. Minh-Duc and D. Wouessidjewe

Cation and Anion Coordination Chemistry of Redox Active Calixarene Macrocyclic Ligand Systems

Paul D. Beer

Functionalization and Application of Calixarenes W. Verboom, R.H. Vreekamp, D.M. Rudkevich and D.N. Reinhoudt

Design Principles for Engineering Conducting Discotic Liquid Crystals

N. Boden, R.J. Bushby. J. Clements, R. Luo and K.J. Donovan

Organic Synthesis and Materials Science M. Baumgarten, U. Bunz, U. Scherf and K. MUllen

vii

xi

xix

1

29

41

59

77

99

119

147

159

viii

New Aspects of Heterocyclic Annulene Chemistry M.P. Cava and Z. Hu

Electrochemical Properties of Fullerenes and Fulerene Derivatives: A Possible Route to Endohedral Complexes

Luis Echegoyen, Francisco Arias and Qingshan Xie

Photoinduced Electron Transfer in Bis-Porphyrin-Stoppered [2)-Rotaxanes

J-C. Chambron, S. Chardon-Noblat, A. Harriman, V. Heitz and J-P. Sauvage

New Materials Based on Highly-Functionalised Tetrathiafulvalene Derivatives

M.R. Bryce, A.S. Batsanov, W. Devonport, J.N. Heaton, J.A.K. Howard, G.J. Marshallsay, A.J. Moore, P.J. Skabara and S. Wegener

189

199

215

235

Design, Synthesis and Properties of Exotic Tetrathiafulvalenes 251 A. Robert and D. Lorey

Novel TTF Derivatives as Components for Conducting CT Complexes 277 J.Y. Becker, E. Aqad, J. Bernstein, A. Ellern, V. Khodorkovsky, T. Regev, L. Shahal, L. Shapiro and C-S. Wang

Tetrathiafulvalenes with Extended Conjugation 295 E. Fanghanel, N. Beye, R. Wegner, J. Bierwisch, R. Herrmann, L. Van Hinh, B. Gabler and K. Strunk

Giant Analogues of Tetrathiafulvalene: Outcome and Prospect 311 A. Gorgues, M. Jubault, A. Belyasmine, M. Salle, P. Frere, V. Morisson andY. Gouriou

Unsymmetrically-Substituted Tetrathiafulvalenes (TTF) as Key 325 Intermediates in the Preparation of Functionalized TTF Derivatives

M. Fourmigue, A. Dolbecq, F.C. Krebs and J. Larsen

From Molecular Structures to Solid State Properties in 333 n-Charge Transfer Salts

P. Delhaes

New Bimetallic Tetrathiafulvalene Building Blocks and Self-Assembled, 349 Two-Dimensional Conductors Derived from Regioregular, Head-to-Tail Coupled Polythiophenes

Richard D. McCullough, John A. Belot and Shawn P. Williams

Author Index

Subject Index

ix

365

367

PARTICIPANTS

Dr. Chantal Andraud Ecole Normale Superieure de Lyon Stereochimie et Interactions Moleculaires 46, Allee d'Italie F-69364 Lyon Cedex 07 France

Mr. Emad Aqad Dept. of Chemistry Ben-Gurion University of the Negev P.O.B. 653 Beer-Sheva Israel

Prof. Jan Becher DeprummentofChe~try

University of Odense Campusvej 55 DK-5230 Odense M Denmark

Prof. K. Bechgaard Dept. of Solid State Physics RIS0 National Laboratory P.O. Box 49 DK-4000 Roskilde Denmark

Prof. J. Y. Becker DepartmentofChe~try

Ben-Gurion Univ. of the Negev P.O. B. 653 IL-84105 Beer-Sheva Israel

xi

Prof. Dr. P. D. Beer University of Oxford Inorganic Chemistry Laboratory South Parks Road Oxford, OXl 3QR UK

Dr. John A. Belot Department of Chemistry Carnegie Mellon University 4400 Fifth Avenue Pittsburgh, PA 15213-3890 USA

Dr. T. Bj0rnholm CISMI, Dept. of Chemistry University of Copenhagen Fruebjergvej 3 DK-2100 Copenhagen Denmark

Prof. Neville Boden Centre for Self-Organising Molecular Systems University of Leeds Leeds LS2 9JT UK

Prof. M. R. Bryce Department of Chemistry University of Durham South Road Durham DHl 3LE UK

xii

Prof. Michael P. Cava Department of Chemistry University of Alabama Tuscaloosa, AL 35487-0336 USA

Dr. J.-C. Chambron Universite Louis Pasteur Lab. de Chim. Organo-Minerale URA au CNRS 422 Institut de Chimie F-67000 Strasbourg Cedex France

Mr. Rasmus P. Clausen Department of Chemistry University of Odense Campusvej 55 DK-5230 Odense M Denmark

Dr. A. W. Coleman CNRS Centre Pharmaceutique F-92296 Chatenay-Malabry France

Dr. Wim Dehaen Katholieke Univ. Leuven Celestynenlaan 200 F B-3001 Heverlee Belgium

Prof. P. Delhaes Centre de Recherche Paul Pascal - CNRS Avenue A" Schweitzer F-33600 PESSAC Cedex France

Mr. Heinz-Josef Deussen CISMI, Dept. of Chemistry University of Copenhagen Fruebjergvej 3 DK-2100 Copenhagen Denmark

Ms. Anne Dolbecq Lab. de Phys. des Solides Universite Paris-Sud Bat. 510, Centre Universitaire F-91405 Orsay Cedex France

Prof. Luis Echegoyen Department of Chemistry University of Miami P.O. Box 249118 Coral Gables, FL 33124-0431 USA

Prof. J. M. Fabre Lab. de Chimie Organique Structurale USRL Place Eugene Bataillon F-34095 Montpellier Cedex 5 France

Prof. E. Fanghcinel Institute of Organic Chemistry Dept. of Chemistry Martin-Luther-Univ. Halle-Wittenberg D-06217 Merseburg, Geusaer Str. Germany

Dr. M. Fourmigue Universite Paris-Sud Lab. de Phys. des Solides Bat. 510, Centre Universitaire F-91405 Orsay Cedex France

Dr. J. Garin Dept. of Organic Chemistry, ICMA University of Zaragoza E-50009 Zaragoza Spain

Prof. Harry W. Gibson Dept. of Chemistry Vrrginia Polytechnic and State University Blacksburg, VA 24061 USA

Xlll

Dr. Carlos Gomez-Garda Dr. Gary Johansson Centre de Recherche Paul Dept. of Macromolecular Science Pascal - CNRS Case Western Reserve University Avenue A. Schweitzer 10900 Euclid Avenue F-33600 Pessac cedex Cleveland, Ohio 44106-7202 France USA

Prof. Alain Gorgues Dr. M. Jubault Universite d' Angers Universite d' Angers Lab. de Chimie Organique Lab. de Chim. Org. - LCOFA Fondamentale et Appliquee Faculte des Sciences 2. Bd Lavoisier 2, Boulevard Lavoisier F-49045 Angers Cedex F-49045 Angers Cedex France France

Mr. Daniel Greve Dr. Mikkel J0rgensen CISMI, Dept. of Chemistry Dept. of Solid State Physics University of Copenhagen Ris0 National Laboratory Fruebjergvej 3 P.O. Box49 DK-2100 Copenhagen DK-4000 Roskilde Denmark Denmark

Dr. Thomas Kruse Hansen Cand.scient. Tme J0rgensen Novo Nordisk A/S Department of Chemistry Novo Nordisk Park University of Odense DK-2760 MAI0v Campusvej55 Denmark DK-5230 Odense M

Denmark Dr. Lothar Hennig University of Leipzig Prof. Olivier Kahn Institute of Organic Chem. Lab. de Cbimie lnorganique Talstrasse 35 CNRS URA420 D-04103 Leipzig Universite de Paris-Sud Germany F-91405 Orsay

France Dr. I. Johannsen Dept. of Solid State Physics Prof. Angel E. Kaifer RIS0 National Laboratory Department of Chemistry P.O. Box 49 University of Maimi DK-4000 Roskilde P.O. Box 249118 Denmark Coral Gables, FL 33124-0431

USA

XIV

Dr. V. Y. Khodorkovski Department of Chemistry Ben-Gurion Univ. of the Negev P.O.B. 653 IL-84105 Beer-Sheva, Israel

Dr. J. Kilburn Department of Chemistry University of Southampton Highfield Southampton, S09 5NH UK

Dr. A. M. Kini Chern. and Materials Science Div. Argonne National Laboratory 9700 S. Cass Av., Build. 200/A125 Argonne, IL 60439-4831 USA

Ms. Gitte Just Kristensen Department of Chemistry University of Odense Campusvej 55 DK-5230 Odense M Denmark

Prof. M.V. Lakshmikantham Department of Chemistry The University of Alabama Box 870336 Tuscaloosa, AL 35487-0336 USA

Mr. Niels B. Larsen CISMI, Dept. of Chemistry University of Copenhagen Fruebjergvej 3 DK-2100 Copenhagen Denmark

Mr. Jesper Lau Department of Chemistry University of Odense Campusvej 55 DK-5230 Odense M Denmark

Mr. P. Leriche Department of Chemistry University of Odense Campusvej 55 DK-5230 Odense M Denmark

Ms. Lene Lomholt Department of Chemistry University of Odense Campusvej 55 DK-5230 Odense M Denmark

Dr. D. Lorey Groupe de Recherches Physicochimie Structurale Universite de Rennes Avenue du General Leclerc F-35042 Rennes Cedex France

Dr. Christine McKenzie Department of Chemistry University of Odense Campusvej 55 DK-5230 Odense Denmark

Prof. Richard D. McCullough Department of Chemistry Carnegie Mellon University 4400 Fifth Avenue Pittsburgh, PA 15213-3890 USA

Dr. Christophe Mingotaud Centre de Recherche Paul Pascal -CNRS Avenue A. Schweitzer F-33600 PESSAC Cedex France

Prof. Klaus Miillen Max-Planck-Institut fi.ir Polymerforschung Ackermannweg 10 D-55128 Mainz Germany

Ms. Pernille M0rk Department of Chemistry University of Odense Campusvej 55 DK-5230 Odense Denmark

Prof. Ojars Neilands Department of Organic Chemistry Riga Technical University 1, Kalku st. LV-1658, Riga PDP, Latvia

Prof. George R. Newkome Department of Chemistry University of South Florida Tampa, FL 33620-7901 USA

Prof. Hans Toftlund Nielsen Department of Chemistry University of Odense Campusvej 55 DK-5230 Odense M Denmark

Mr. Mohammad Nouri Department of Chemistry University of Odense Campusvej 55 DK-5230 Odense Denmark

Dr. R.M. Olk Department of Chemistry Universitat Leipzig Talstrasse 35 D-04103 Leipzig Germany

Dr. Lacene Ouahab LCIM CNRS URA 1495 Universite de Rennes F-35042 Rennes Cedex France

Mrs. Ofra Paztal-Levi Department of Chemistry Ben-Gurion Univ. of the Negev P.O. B. 653 IL-84105 Beer-Sheva Israel

Prof. Virgil Percec Dept. of Macromolecular Science Case Western Reserve University Cleveland, Ohio 44106-7202 USA

Mr. A. Puplovskis Department of Organic Chemistry Riga Technical University 1, Kalku st. LV-1658, Riga PDP, Latvia

Miss Elena Ramos Institut de Ciencia de Materials de Barcelona - CSIC Campus de la UAB E-08193 Bellaterra Spain

Ms. Karen Margrethe Rasmussen Department of Chemistry University of Odense Campusvej 55 DK-5230 Odense Denmark

Miss Tal Regev Department of Chemistry Ben-Gurion Univ. of the Negev P.O. B. 653 IL-84105 Beer-Sheva Israel

Mr. Knut Reiner Department of Chemistry Universitat Leipzig Talstrasse 35 D-04103 Leipzig Germany

XV

xvi

Prof. A. Robert Groupe de Recherches Physicochimie Structurale Universite de Rennes Avenue du General Leclerc F-35042 Rennes Cedex France

Dr. Dmitri Rudkevich University of Twente P.O. Box 217 7500 AE Enschede The Netherlands

Dr. C. Rovira Institut de Ciencia de Materials de Barcelona- CSIC Campus de Ia UAB E-08193 Bellaterra Spain

Mr. Daniel Ruiz Inst. de Ciencia de Materials Barcelona- CSIC Campus de Ia UAB E-08193 Bellaterra Spain

Prof. M. Salle Universite d' Angers Lab. de Chim. Org.- LCOFA 2, Boulevard Lavoisier F-49045 Angers cedex France

Prof. Kjeld Schaumburg CISMI, Dept. of Chemistry University of Copenhagen Fruebjergvej 3 DK-2100 Copenhagen Denmark

Mr. Niels Christian Schi0dt CISMI, Dept. of Chemistry University of Copenhagen Fruebjergvej 3 DK-2100 Copenhagen Denmark

Prof. J. Simon Lab. de Chimie et Electrochimie desMateriaux Moleculaires - ESPI 10, rue Vauquelin F-75231 Paris Cedex 05 France

Mr. Klaus Brek Simonsen Department of Chemistry University of Odense Campusvej 55 DK-5230 Odense Denmark

Prof. J. F. Stoddart University of Birmingham School of Chemistry Edgbaston Birmingham B15 2TI UK

Mr. Niels Svenstrup Department of Chemistry University of Odense Campusvej 55 DK-5230 Odense Denmark

Prof. A. E. Underhill Department of Chemistry Univ. College of North Wales Bangor, Gwynedd LL57 2UW UK

Dr. Santiago Uriel Univ. Paris-Sud Lab. de Physique des Solides Bat. 510, Centre Universitaire F-91405 Orsay cedex France

Mr. Michael Wagner Department of Chemistry Universitat Leipzig Talstrasse 35 D-04103 Leipzig Germany

Dr. Chang-Sheng Wang Department of Chemistry Ben-Gurion Univ. of the Negev P.O.B. 653 IL-84105 Beer-Sheva Israel

Dr. James K. Young Dept. of Chemistry Univ. of Illinois at Urbana-Champaign 479 Roger Adams Laboratory Urbana, IL 61801 USA

Mr. Stephan Zeltner Inst. of Inorganic Chemistry University of Leipzig Talstrasse 35 D-04103 Leipzig Germany

xvii

;>< S:

Part

icip

an

ts

in

the

NATO

AR

W

on M

ole

cula

r E

ng

inee

rin

g f

or

Adv

ance

d M

ate

rials

INTRODUCTION

The present book is an edited version of the main lectures given at the NATO Advanced Research Workshop entitled "Molecular Engineering for Advanced Mate­rials". The interpretation of the term "Molecular Engineering" turned out to be some­what different for different scientists. Likewise "Advanced Materials" imply an evalua­tion against a predefined scale, which is not generally known. The meeting was concluded with a session where the various interpretations were debated. A short excerpt of this discussion will be given here to indicate the outline of the field without an attempt to make a precise definition.

An important aspect of Molecular Engineering is "property directed synthesis" of large molecules and molecular assemblies. The development in this field of supramolecular chemistry at present may be compared to the rapid expansion in the dye industry a century ago and to the expansion in the drug industry during the last fifty years. The synthetic expertise has advanced to at state which allows the assembly of supramolecules containing thousands of atoms. The "Legobox", with molecular building blocks, already contains a large number of different units, with which one can try to build molecular devices in two or three dimensions. At the workshop new available tetrathiafulvalene (TIP) building blocks were described by several participants. They include: 3D TTF; Ribbons of TTF; Giant TTF units; Macrocyclic TTF; Dendritic TTF and Quantum dot TTF. This example is one out of many. The expansion in the field is driven by the appearance of new molecular building blocks and by the improved understanding of the rules for joining them not only in covalently bonded structures but also using non-covalently bonded structures in the design of new molecular devices. In the effort to be able to synthesize nanometer sized objects the principle of selfassembly emerges as essential for the fast, simple and reliable route to the final product. It is important here to stress that Molecular Engineering is experimentally driven and multidisciplinary due to its complexity. To focus the activity it must, however, always be guided by the interest in a class of properties to be optimized. When designing a new project in this field it is necessary to remember that serendipity is very important.

Another aspect of Molecular Engineering is the transition from supramolecules to materials. This is a very active scientific field emerging and it will be of paramount importance in the future. As it stands at present, scientists have not yet succeeded in demonstrating single molecules functioning as devices. The obstacles to overcome are primarily technical and require close cooperation between chemists and engineers. When solved, an almost endless list of molecular based devices can be designed, only limited by imagination.

xix

XX

Advanced materials based on molecular building blocks will be expected to show better or new properties. These may include better processability like soluble magnetic materials, or they may show favorable transparency in important communication bands. More intricate is the balancing of molecular properties and solid state properties as they can emerge in loosely coupled molecular materials. The flexibility in design of supramolecular materials makes it furthermore possible to couple two or several optimized properties into the same material, a task which would be impossible by traditional means.

The change in emphasis from bulk materials to individual supramolecules requires new methods for analysis and characterization of properties. Classical spectroscopic and diffraction techniques are indispensable but not sufficient. When available the new methods will provide new insight and new inspiration for the synthesis and materials preparation.

The Molecular Engineering of Advanced Materials is critically dependant on the multidisciplinary education of young scientists. It was a common concern among the participants that the curriculum today at most universities does not reflect this multidisciplinarity. At the PhD level it will be urgent to introduce supramole­cular chemistry, materials preparation and characterization and combine this with training in solid state physics and selfassembly based on biological principles. The entire program should be based on the newest results. It is hoped that the present volume of the NATO Advanced Workshop reports will provide some inspiration for such an education.

The organizing committee would like to express its sincere acknowledgement for the general support from NATO ARW and the additional support from the Danish National Research Council, Novo Nordisk Fund, Munkem~:llle Fund, and Odense University.

Finally, we would like to express our appreciation to all the students, who were helping during the entire meeting, and a special thank to the secretary Annette Frydendahl for her assistance.

Autumn 1994 Jan Becher Kjeld Schaumburg