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Jean-Marie Lehn

Supramolecular Chemistry
 Related Titles from VCH
Jean-Marie Lehn

C. St. Cooper (ed.)

Crown Compounds.
Toward Future Applications
ISBN 3-527-28073-1
Supramolecular
B. Dietrich, P. Viout, J.-M. Lehn
Macrocyclic Chemistry. Aspects of Organic
and Inorganic Supramolecular Chemistry
Chemistry
ISBN 3-527-28330-7

J. Fuhrhop, G. Penzlin Concepts and Perspectives

Organic Synthesis. Concepts, Methods,
Starting Materials
Second, Revised and Enlarged Edition European Molecular
With a Foreword by E. J. Corey Biology Laboratory
Hardcover ISBN 3-527-29086-9 \ Postfach 10 22 09
Softcover ISBN 3-527-29074-5 D-69012 Heidelberg
Tei.06221-3810
K.C. Nicolaou, E. J. Sorensen
Classics in Total Synthesis A Personal Account
Hardcover ISBN 3-527-29231 -4
Softcover ISBN 3-527-29284-5
Built upon the

George Fisher Baker Lectures Lezioni Lincee

in Chemistry Accademia N azionale
at Cornell University dei Lincei
Roma
© VCH Verlagsgesellschaft mbH. D-69451 Weinheim (Bundesrepublik Deutschland), 1995

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ISBN 3-527-29311-6 (Softcover) ISBN 3-527-29312-4 (Hardcover) Basel • Cambridge • Tokyo
VI Preface

This is also the occasion to fulfil, although belatedly, the request for a write up of
the Baker Lectures given at Cornell University in 1978 (!)and of the Lezioni Lincee Contents
held at the Accademia Nazionale dei Lincei and at the University of Rome in 1992.
It is long overdue, but it certainly profits from the much firmer basis, the much
stronger body and the much broader scope that the field of supramolecular chem-
istry has acquired. I thank my colleagues at these Institutions for their warm hospi-
tality during my stay with them and for their patience!
I wish to express my gratitude to the numerous research groups with which we
have enjoyed collaborating over the years and my deep appreciation to all those
around the world who have contributed to make supramolecular chemistry what it
has become and who will keep it alive and growing in the future.
I thank the Universite Louis Pasteur, the College de France, the Centre National
de la Recherche Scientifique and the Science Programmes of the European Com-
munity for providing the local intellectual environment and the financial support of
our work. 1 From Molecular to Supramolecular Chemistry . . . 1
I am much indebted to Dr. Bernard Dietrich for his competent and scrupulous
eye in reading the draft and in checking the references and illustrations, to Doris Concepts and Language of Supramolecular Chemistry 4
Biltz for her expert and efficient typing as well as to Thierry Bataille, Serge Wechs-
ler and Robert Weidmann for generating the drawings. 2 Molecular Recognition . . . . . . . . . . . . 11
2.1 Recognition, Information, Complementarity 11
Finally, highest credit goes of course to my 200 or so coworkers from many coun- 2.2 Molecular Receptors - Design Principles . . 14
tries who, over the years, have performed with skill and dedication the work rea- 2.3 Spherical Recognition - Cryptates of Metal Cations 17
lised and provided the stimulating international and cross-cultural atmosphere that 2.4 Tetrahedral Recognition by Macrotricyclic Cryptands 24
is a major attraction of life as a scientist. 2.5 Recognition of Ammonium Ions and Related Substrates 26
2.6 Binding and Recognition, of Neutral Molecules . . . . . 29
Strasbourg, April1995 Jean-Marie Lehn
3 Anion Coordination Chemistry and the Recognition of Anionic
Substrates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31

4 Coreceptor Molecules and Multiple Recognition . 37

4.1 Dinuclear and Polynuclear Metal Ion Cryptates . . . . . . . . . . 39
4.2 Linear Recognition of Molecular Length by Ditopic Coreceptors 41
4.3 Heterotopic Coreceptors - Cyclophane Receptors, Amphiphilic
Receptors, Large Molecular Cages. . . . . . . . . . . . . . . . . . 43
4.4 Multiple Recognition in Metalloreceptors 50
4.5 Supramolecular Dynamics . . . . . . . . . 51
..
5 Supramolecular Reactivity and Catalysis 55
5.1 Catalysis by Reactive Macrocyclic Cation Receptor Molecules 57
5.2 Catalysis by Reactive Anion Receptor Molecules . . . . . . . 59
5.3 Catalysis with Cyclophane Type Receptors 61
 -
VIII Con tents Contents IX

5.4 Supramolecular Metallocatalysis . . . . . . . 61 8.4.2 Ion-Responsive Monolayers . . . .. . . . . . . . . . . . . . .. . . 116

5.5 Cocatalysis: Catalysis of Synthetic Reactions 62 8.4.3 "Bouquet"-Type Molecules and the "Chundle" Approach
5.6 Biomolecular and Abiotic Catalysis . . . 66 to Molecular Channels . . 118
8.4.4 Molecular Protonics . . . . . . . . . . . . . . . . . 121
6 Transport Processes and Carrier Design 69 8.4.5 Ion and Molecule Sensors . . . . . . . . . . . . .. . 123
8.5 Switching Devices and Signals. Semiochemistry 124
6.1 Carrier-Mediated Transport . . . . . . . 70 8.5.1 Switching Devices. Signals and Information . 124
6.2 Cation Transport Processes- Cation Carriers . 71 8.5.2 Photoswitching Devices . . . . . . . . . . . 127
6.3 Anion Transport Processes -Anion Carriers . . 73 8.5.3 Electroswitching Devices . . . . . . . . . . . 131
6.4 Coupled Transport Processes . . . . . . . . . . 75 8.5.4 Switching of Ionic and Molecular Processes . 133
6.4.1 Electron-Coupled Transport in a Redox Gradient 75 8.5.5 Mechanical Switching Processes . . . . . . . 135
6.4.2 Proton-Coupled Transport in a pH Gradient 76
6.4.3 Light-Coupled Transport Processes . . 77 9 Self-Processes- Programmed Supramolecular Systems 139
6.5 Transfer via Transmembrane Channels . . . . 79
9.1 Self-Assembly. Self-Organization . . . . . 139
7 From Supermolecules to Supramolecular Assemblies 81 9.2 Programmed Supramolecular Systems . . . 143
9.3 Self-Assembly of Inorganic Architectures . 144
7.1 Heterogeneous Molecular Recognition. Supramolecular Solid 9.3.1 Self-Assembly of Double-Helical and Triple-Helical Metal
Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82 Complexes: The Helicates . . . . . . . . . . . . . . . . . .
7.2 From Endoreceptors to Exoreceptors. Molecular Recognition at
146
9.3.2 Multicomponent Self-Assembly . . . . . . . . . . . . . . . 154
Surfaces . . . . . . . . . . . . . . . . . . . . . . 83 9.3.3 Supramolecular Arrays of Metal Ions. Racks, Ladders, Grids 157
7.3 Molecular and Supramolecular Morphogenesis 85 9.4 Self-Assembly of Organic Supramolecular Structures . . . . 161
7.4 Supramolecular Heterogeneous Catalysis . 86 9.4.1 Self-Assembly by Hydrogen-Bonding. Janus Molecules .. . 161
9.4.2 Molecular Recognition-Directed Assembly of Organized Phases . 165
8 Molecular and Supramolecular Devices . . . . . . . . . . . . . 89 9.4.3 Supramolecular Polymer Chemistry . . . . . . . . . . . . . . . . . 173
8.1 Molecular Recognition, Information and Signals. Semiochemistry 90 9.4.4 Molecular Recognition-Directed Self-Assembly of Ordered Solid-
8.2 Supramolecular Photochemistry. Molecular and Supramolecular State Structures . . . . . . . . . . . . . . . . . 174
Photonic Devices . . . . . . . . . . . . . . . . . 91 9.4.5 Physico-Chemical Methods of Investigation . . . . . . 179
8.2.1 Light Conversion and Energy Transfer Devices 92 9.5 Self-Recognition. Instructed System Paradigm . . . . . 180
8.2.2 Photosensitive Molecular Receptors . . . . . . . 95 9.6 Supramolecular Synthesis, Assistance and Replication . 184
8.2.3 9.6.1 Supramolecular Synthesis . . . . . . . 185
Photoinduced Electron Transfer in Photoactive Devices . 97
8.2.4 9.6.2 Supramolecular Assistance to Synthesis 185
Photoinduced Reactions in Supramolecular Species . . . . 99
9.6.3 Replication. Self-Replication . . . . . . 188
8.2.5 Non-Linear Optical Properties of Supramolecular Species. 100
9.7 Supramolecular Chirality and Self-Assembly
8.2.6 Supramolecular Effects in Photochemical Hole Burning . 103 190
9.8 Supramolecular Materials. Nanochemistry
8.3 Molecular and Supramolecular Electronic Devices 104 193
9.9 Chemionics . . . . . . . . . . . . . . . . .
8.3.1 Supramolecular Electrochemistry . . . . . . . . 105 195
8.3.2 Electron Conducting Devices. Molecular Wires 106 10
8.3.3 Perspectives . . . . . . . . . . . . . . . . . 199
Polarized Molecular Wires. Rectifying Devices . . '·' 111
8.3.4 Modified and Switchable Molecular Wires . . . 111 10.1 From Structure to Information. The Challenge of Instructed
8.3.5 Molecular Magnetic Devices . . . . . . . . . . 113 Chemistry . . . . . . . . . . . . . . . . . . . 199
8.4 Molecular and Supramolecular Ionic Devices 113 10.2 Steps Towards Complexity . . . . . . . . . .
10.3
201
8.4.1 Tubular Mesophases . . . . . . . . . . . . . . . 115 Chemistry and Biology, Creativity and Art . 204
X Contents

Bibliography and Notes 207

1 From Molecular to Supramolecular
Appendix . . . . . . . . . 259
Chemistry
Illustration Acknowledgments 261

Index . . . . . . . . . . . . . . . 263

In the beginning was the Big Bang, and physics reigned. Then chemistry came along
at milder temperatures; particles formed atoms; these united to give more and more
complex molecules, which in turn associated into aggregates and membranes, defin-
ing primitive cells out of which life emerged.
Chemistry is the science of matter and of its transformations, and life is its
highest expression. It provides structures endowed with properties and develops
processes for the synthesis of structures. It plays a primordial role in our under-
standing of material phenomena, in our capability to act upon them, to modify
them, to control them and to invent new expressions of them.
Chemistry is also a science of transfers, a communication centre and a relay be-
tween the simple and the complex, between the laws of physics and the rules of life,
between the basic and the applied. If it is thus defined in its interdisciplinary rela-
tionships, it is also defined in itself, by its object and its method.
In its method, chemistry is a science of interactions, of transformations and of
models. In its object, the molecule and the material, chemistry expresses its creativ-
ity. Chemical synthesis has the power to produce new molecules and new materials
with new properties. New indeed, because they did not exist before being created
by the recomposition of atomic arrangements into novel and infinitely varied com-
binations and structures [1.1 ].
For more than 150 years, since the synthesis of urea by Friedrich Wohler in 1828
[1.2], molecular chemistry has developed a vast array of highly sophisticated and
powerful methods for the construction of ever more complex molecular structures
.• by the making or breaking of covalent bonds between atoms in a controlled and pre-
cise fashion.
Organic synthesis grew rapidly and masterfully, leading to a whole series of bril-
liant achievements, the great syntheses of the last SO years, where elegance of stra-
tegy combined with feats of efficiency and selectivity. There is a long way from