Jean-Marie Lehn

Supramolecular Chemistry

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Jean-Marie Lehn

Supramolecular Chemistry

A Personal Account

Concepts and Perspectives

Built upon the

European Molecular Biology Laboratory \ Postfach 10 22 09

D-69012 Heidelberg Tei.06221-3810

George Fisher Baker Lectures in Chemistry

Lezioni Lincee Accademia N azionale dei Lincei at Cornell University Roma

Weinheim ·New York 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 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 chem­istry has acquired. I thank my colleagues at these Institutions for their warm hospi­tality 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 Com­munity for providing the local intellectual environment and the financial support of our work.

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 Biltz for her expert and efficient typing as well as to Thierry Bataille, Serge Wechs­ler and Robert Weidmann for generating the drawings.

Finally, highest credit goes of course to my 200 or so coworkers from many coun­tries who, over the years, have performed with skill and dedication the work rea­lised and provided the stimulating international and cross-cultural atmosphere that is a major attraction of life as a scientist.

Strasbourg, April1995 Jean-Marie Lehn

..

Contents

1 From Molecular to Supramolecular Chemistry . . .

Concepts and Language of Supramolecular Chemistry

2 Molecular Recognition . . . . . . . . . . . .

2.1 2.2 2.3 2.4 2.5 2.6

Recognition, Information, Complementarity Molecular Receptors - Design Principles . . Spherical Recognition - Cryptates of Metal Cations Tetrahedral Recognition by Macrotricyclic Cryptands Recognition of Ammonium Ions and Related Substrates Binding and Recognition, of Neutral Molecules .....

1

4

11

11 14 17 24 26 29

3 Anion Coordination Chemistry and the Recognition of Anionic Substrates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31

4 Coreceptor Molecules and Multiple Recognition . 37

4.1 4.2 4.3

4.4 4.5

Dinuclear and Polynuclear Metal Ion Cryptates . . . . . . . . . . 39 Linear Recognition of Molecular Length by Ditopic Coreceptors 41 Heterotopic Coreceptors - Cyclophane Receptors, Amphiphilic Receptors, Large Molecular Cages. . . . . . . . . . . . . . . . . . 43 Multiple Recognition in Metalloreceptors 50 Supramolecular Dynamics . . . . . . . . . 51

5 Supramolecular Reactivity and Catalysis 55 5.1 5.2 5.3

Catalysis by Reactive Macrocyclic Cation Receptor Molecules 57 Catalysis by Reactive Anion Receptor Molecules . . . . . . . 59 Catalysis with Cyclophane Type Receptors 61

VIII

5.4 5.5 5.6

6

6.1 6.2 6.3 6.4 6.4.1 6.4.2 6.4.3 6.5

7

7.1

7.2

7.3 7.4

8

8.1 8.2

8.2.1 8.2.2 8.2.3 8.2.4 8.2.5 8.2.6 8.3 8.3.1 8.3.2 8.3.3 8.3.4 8.3.5 8.4 8.4.1

Contents

Supramolecular Metallocatalysis . . . . . . . Cocatalysis: Catalysis of Synthetic Reactions Biomolecular and Abiotic Catalysis . . .

Transport Processes and Carrier Design

Carrier-Mediated Transport ...... . Cation Transport Processes- Cation Carriers . Anion Transport Processes -Anion Carriers . . Coupled Transport Processes . . . . . . . . . . Electron-Coupled Transport in a Redox Gradient Proton-Coupled Transport in a pH Gradient Light-Coupled Transport Processes . . Transfer via Transmembrane Channels . . . .

From Supermolecules to Supramolecular Assemblies

Heterogeneous Molecular Recognition. Supramolecular Solid Materials .................... . ........ . From Endoreceptors to Exoreceptors. Molecular Recognition at Surfaces ..... ... ............. . Molecular and Supramolecular Morphogenesis Supramolecular Heterogeneous Catalysis .

Molecular and Supramolecular Devices . . . . . . . . . . . . .

Molecular Recognition, Information and Signals. Semiochemistry Supramolecular Photochemistry. Molecular and Supramolecular Photonic Devices . . . . . . . . . . . . . . . . . Light Conversion and Energy Transfer Devices Photosensitive Molecular Receptors . . . . . . . Photoinduced Electron Transfer in Photoactive Devices . Photoinduced Reactions in Supramolecular Species . . . . Non-Linear Optical Properties of Supramolecular Species. Supramolecular Effects in Photochemical Hole Burning . Molecular and Supramolecular Electronic Devices Supramolecular Electrochemistry . . . . . . . . Electron Conducting Devices. Molecular Wires Polarized Molecular Wires. Rectifying Devices . Modified and Switchable Molecular Wires . . . Molecular Magnetic Devices . . . . . . . . . . Molecular and Supramolecular Ionic Devices Tubular Mesophases . . . . . . . . . . . . . . .

' . '·

61 62 66

69

70 71 73 75 75 76 77 79

81

82

83 85 86

89

90

91 92 95 97 99

100 103 104 105 106 111 111 113 113 115

-

8.4.2 8.4.3

8.4.4 8.4.5 8.5 8.5.1 8.5.2 8.5.3 8.5.4 8.5.5

9

9.1 9.2 9.3 9.3.1

9.3.2 9.3.3 9.4 9.4.1 9.4.2 9.4.3 9.4.4

9.4.5 9.5 9.6 9.6.1 9.6.2 9.6.3 9.7 9.8 9.9

10

10.1

10.2 10.3

Contents

Ion-Responsive Monolayers ... .. ........... . "Bouquet"-Type Molecules and the "Chundle" Approach to Molecular Channels . . Molecular Protonics . . . . . . . . . . . . . . . . . Ion and Molecule Sensors . . . . . . . . . . . . .. . Switching Devices and Signals. Semiochemistry Switching Devices. Signals and Information . Photoswitching Devices . . . . . . . . . . . Electroswitching Devices . . . . . . . . . . . Switching of Ionic and Molecular Processes . Mechanical Switching Processes . . . . . . .

Self-Processes- Programmed Supramolecular Systems

Self-Assembly. Self-Organization ..... Programmed Supramolecular Systems . . . Self-Assembly of Inorganic Architectures . Self-Assembly of Double-Helical and Triple-Helical Metal Complexes: The Helicates . . . . . . . . . . . . . . . . . . Multicomponent Self-Assembly ... . .......... . Supramolecular Arrays of Metal Ions. Racks, Ladders, Grids Self-Assembly of Organic Supramolecular Structures ... . Self-Assembly by Hydrogen-Bonding. Janus Molecules .. .

. .. . .

Molecular Recognition-Directed Assembly of Organized Phases . Supramolecular Polymer Chemistry ................ . Molecular Recognition-Directed Self-Assembly of Ordered Solid­State Structures . . . . . . . . . . . . . . . . . Physico-Chemical Methods of Investigation . . . . . . Self-Recognition. Instructed System Paradigm . . . . . Supramolecular Synthesis, Assistance and Replication . Supramolecular Synthesis . . . . . . . Supramolecular Assistance to Synthesis Replication. Self-Replication ..... . Supramolecular Chirality and Self-Assembly Supramolecular Materials. Nanochemistry Chemionics . . . . . . . . . . . . . . . . .

Perspectives . . . . . . . . . . . . . . . . .

From Structure to Information. The Challenge of Instructed Chemistry .................. . Steps Towards Complexity . . . . . . . . . . Chemistry and Biology, Creativity and Art .

IX

116

118 121 123 124 124 127 131 133 135

139

139 143 144

146 154 157 161 161 165 173

174 179 180 184 185 185 188 190 193 195

199

199 201 204

X Contents

Bibliography and Notes 207

Appendix ........ . 259

Illustration Acknowledgments 261

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

.•

1 From Molecular to Supramolecular Chemistry

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, defin­ing 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 under­standing 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 be­tween 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 rela­tionships, 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 creativ­ity. 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 com­binations 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 pre­cise fashion.

Organic synthesis grew rapidly and masterfully, leading to a whole series of bril­liant achievements, the great syntheses of the last SO years, where elegance of stra­tegy combined with feats of efficiency and selectivity. There is a long way from