From Non-Covalent Assemblies to Molecular Machines E-Book

• Herausgeber: Wiley-VCH
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 805

Veröffentlichungsjahr: 2011

Beschreibung

Based on the Solvay conference, which gathers the leading scientists in the field, this monograph collects review articles from the six topics of the conference, while also including comments, discussions and debates obtained during the conference.
The issues discussed at this landmark conference were:
* Noncovalent Assemblies: Design and Synthesis
* Template Synthesis of Catenanes and Rotaxanes
* Molecular Machines Based on Catenanes and Rotaxanes
* Molecular Machines Based on Non-Interlocking Molecules
* Towards Molecular Logics and Artificial Photosynthesis
* From Single Molecules to Practical Devices
and the authors add their personal views on the future of each of their own research areas.
Novel reading for organic, inorganic and polymer chemists, as well as materials scientists.

Leseprobe

Contents

Preface

List of Contributors

Description

Opening Session

The International Solvay Institutes

Solvay Scientific Committee for Chemistry

21st Solvay Conference on Chemistry

Part One Noncovalent Assemblies: Design and Synthesis

1Introduction and Definition of Noncovalent AssembliesJulius Rebek Jr

References

2Noncovalent Assemblies: Design and SynthesisMakoto Fujita and Takashi Murase

2.1 Introduction

2.2 Landmarks in Self-Assembly Fields

2.3 Hydrogen-Bonded Assemblies

2.4 Coordination Assemblies

2.5 Function Through Architecture

2.6 Conclusions

References

3 Discussion 1.AChairman: Julius Rebek Jr

4 Noncovalent Synthesis of Molecular ReceptorsDavid N. Reinhoudt

4.1 Introduction

4.2 Noncovalent Synthesis

4.3 Supramolecular Chirality

4.4 Optical Amplification in Dynamic Supramolecular Systems

Acknowledgments

References

5Cucurbiturils: New Players in Noncovalent AssemblyKimoon Kim

Acknowledgments

References

6Comment on the Possible Presence of Bubbles Inside Self-Assembled Molecular CagesJosef Michl

References

7Discussion 1.BChairman: Julius Rebek Jr

Part Two Template Synthesis of Catenanes and Rotaxanes

8A Short History of the Mechanical BondJohn-Carl Olsen, Kirsten E. Griffiths, and J. Fraser Stoddart

8.1 Introduction

8.2 Donor/Acceptor Templated Systems

8.3 Charged Hydrogen Bond-Templated Systems

8.4 Anion-Templated Synthesis

8.5 Neutral Hydrogen Bond-Templated Systems

8.6 Metal-Containing Catenanes and Rotaxanes

8.7 Solvophobically Driven Templation

8.8 Applications

8.9 Conclusions

References

9 Discussion 2.AChairman: Fritz Vögtle

10 Dynamic Combinatorial Approaches to CatenanesJeremy K. M. Sanders

Notes Added After the Conference

References

11Discussion 2.BChairman: Fritz Vögtle

Part Three Molecular Machines Based on Catenanes and Rotaxanes

12Molecular Machines Based on Rotaxanes and CatenanesVincenzo Balzani, Alberto Credi, and Margherita Venturi

12.1 Introduction

12.2 Molecular Machines: History and Overview

12.3 Molecular Machines Based on Rotaxanes

12.4 Molecular Machines Based on Catenanes

12.5 Performing Functions with Molecular Machines

12.6 Perspectives

Acknowledgments

References

13 Discussion 3.AChairman: David A. Leigh

14 Rearrangement of a Surface-Deposited [2]catenane by Coordination to Copper(I) at the Single-Molecule LevelJean-Pierre Sauvage

Conclusions

References

15A Toroidal Oxidation CatalystAlan E. Rowan, Johannes A.A.W. Elemans, and Roeland J.M. Nolte

References

16Discussion 3.BChairman: David A. Leigh

Part Four Molecular Machines Based on Non-Interlocking Molecules

17Synthetic Molecular Machines Based on Non-Interlocked Systems: From Concept to ApplicationsWesley R. Browne, Dirk Pijper, Michael M. Pollard, and Ben L. Feringa

17.1 Introduction

17.2 Design Concepts [11]

17.3 Synthetic Molecular Rotors

17.4 Synthetic Molecular Motors and Machines

17.5 Molecular Machines: Putting Motors to Work

17.6 Molecular Motors at Work

17.7 Conclusions and Outlook

References

18 Discussion 4.AChairman: Takuzo Aida

19 Comment on Molecular Machines Based on Non-Interlocking Molecules (Other Than Catenanes and Rotaxanes)Josef Michl

References

20A Few Hints Towards Artificial Active Macroscopic SystemsJacques Prost

20.1 Active Molecules

20.2 Active Gels

20.3 Expected Properties

Acknowledgments

References

21Fluctuation Theorem, Nonequilibrium Work, and Molecular MachinesPierre Gaspard

21.1 Introduction

21.2 Fluctuation Theorem

21.3 Nonequilibrium Work Relations

21.4 Application to the F1-ATPase Molecular Motor

21.5 Perspectives

21.6 Note Added after the Conference

Acknowledgments

References

22Discussion 4.BChairman: Takuzo Aida

Part Five Towards Molecular Logics and Artificial Photosynthesis

23 Chairman’s CommentsA. Prasanna de Silva

References

24 Towards Molecular Logic and Artificial PhotosynthesisDevens Gust, Thomas A. Moore, and Ana L. Moore

24.1 Introduction

24.2 Artificial Photosynthesis

24.3 Molecular Logic

24.4 Final Comments

References

25 Discussion 5.AChairman: A. Prasanna de Silva

26 Artificial Photosynthesis: Oxygen Evolution from Photochemical Water SplittingVincenzo Balzani

26.1 Introduction

26.2 Oxygen Evolution

26.3 Lessons from Nature

26.4 Proton-Coupled Electron Transfer

References

27Potential Applications of Molecular LogicAlberto Credi

27.1 Introduction

27.2 Discussion

Acknowledgments

References

28Discussion 5.BChairman: A. Prasanna de Silva

Part Six From Single Molecules to Practical Devices

29From Single Molecules to Practical DevicesJean-Pierre Launay

29.1 Introduction

29.2 Devices Based on Mechanical Effects

29.3 Devices Based on Electronic Effects

29.4 Devices Based on a Combination of Mechanical and Electronic Effects

29.5 Conclusions

Acknowledgment

References

30 Discussion 6.AChairman: Enrico Dalcanale

31 A Spring-Loaded DeviceDariush Ajami and Julius Rebek Jr

Notes After the Conference

Acknowledgments

References

32From Electrochemically-Driven Conformational Polymeric States to Macroscopic Sensing and Tactile MusclesToribio F. Otero

References

33Controlling Self-Assembly in Space and TimeBen L. Feringa

33.1 Introduction

33.2 Low-Molecular-Weight Gelators

33.3 Dynamic Control of Gelation

33.4 Concluding Remarks

References

34Discussion 6.BChairman: Enrico Dalcanale

Index

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The Editors

Prof. Jean-Pierre SauvageUniversité de StrasbourgInstitut de Chimie4, rue Blaise Pascal67070 Strasbourg CedexFrance

Prof. Pierre GaspardUniversité Libre de BruxellesCenter for Nonlinear Phenomena andComplex SystemsCode Postal 231, Campus Plaine1050 BrusselsBelgium

Cover ImageThe drawing was prepared by Alex Bosoy, a graphic artist working in the Mechanostereo chemistry group (Northwestern University, USA). His contribution is gratefully acknowledged.

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Preface

It was a great honor and a real pleasure to chair the 21st Solvay Conference on Chemistry. The prestigious Solvay Conferences on Physics or on Chemistry are all known by the various scientific communities as major events, with a historical impact that is universally recognized. It is obvious to all of us that these conferences had a strong influence on the way physics and chemistry evolved during the course of the past hundred years or so. The spirit and the organization of the conference on chemistry “From Monovalent Assemblies to Molecular Machines” were in accordance with those of the previous conferences. The format was indeed unique: no classical lectures, a pre-eminence of questions and comments and, as a testimony for the widest possible community and for the future scientists interested in the fields discussed during the event, detailed proceedings gathering the various general lectures (“reports”), short presentations (“prepared comments”) and, last but not least, discussions on the prepared comments.

The theme of the Conference was relatively wide, since, a priori, noncovalent assemblies have almost no relationship with controlled dynamic systems (molecular machines). However, at the same time it was relatively focused since, historically, these two fields are tightly linked. The first area is an important subfield of supramolecular chemistry, the development of which has been spectacular during the course of the past 30 years or so. In the particular context of the Conference, transition metals and hydrogen bonds played a special role. The second field, related to molecular motion, is more recent and, to a large extent, has derived from the flourishing field of interlocking compounds (“catenanes and rotaxanes”), the synthesis of which has undergone a spectacular revival during the past 20 years or so. Of course, the creation of interlocking ring structures relies on the ability of molecular chemists to assemble precisely defined multicomponent edifices before making the desired catenanes or analogous species, which was the first topic of the conference.

Functional interlocking compounds–the constitutive elements of which are held together only by “mechanical bonds” rather than covalent bonds–are conceptually particularly well adapted to the study of large-amplitude molecular movements, as the various fragments of catenanes and rotaxanes can move with almost no constraints. A ring can spin around the axle on which it has been threaded, and it can also glide over large distance along the same axis.

Triggering and studying molecular motion is not restricted to interlocking systems. In this context, noninterlocking compounds have also turned out to be of high interest, especially as far as rotary motions are concerned. For both classes of molecules, ingenious chemists have been able to set given fragments of the molecule in motion by using various types of stimulus (light pulse, electrochemical signal, heat, modification of the solvent, etc.). The relation between molecular biology and the numerous motor proteins found in Nature is obvious, as is the connection to physics and Brownian molecular machines, which are of utmost importance in biology.

The use of complex molecular systems, which are able to behave as switches or to display novel properties in relation to molecular logic or artificial photosynthesis, seems to be promising and, even if these research topics are not strictly speaking part of the molecular machine field, they were sufficiently close from a conceptual viewpoint to form part of the themes discussed during the Conference. The high level of interaction between the scientists classified as belonging to a given subfield was a demonstration that it is indeed important to allow various communities to meet and work together.

Finally, a critical point is to know whether applications might be expected in the near future or, at least, to consider possibilities related to practical devices. Some of us have already started to envision important applications, and also to realize highly promising devices from a practical standpoint. It was important to compare the points of view of these investigators with those of more basic-science-oriented researchers. Single-molecular devices, as well as ordered or condensed states of matter consisting of the various molecular systems discussed during the Conference, are certainly to be considered with respect to various applications. Consequently, a special session was devoted to single molecules and their potential, mostly in relation to information storage and processing.

All of the participants at the 21st Solvay Conference on Chemistry are extremely grateful to the Solvay family for their very generous support. The tradition started by this family so long ago is highly beneficial to the scientific community in general, as the Conferences have a scientific impact that goes much beyond the meeting itself. In addition to the generous sponsors whose support made the Conference possible, I would also like to thank all of the participants for their great contributions, as well as the younger colleagues who took care of all the practical aspects of the conference, who gathered the various written reports and comments, and who transcribed the oral presentations, comments, questions and answers. Without their important contribution, the preparation of this book would never have been possible.

Jean-Pierre Sauvage

List of Contributors

Dariush AjamiThe Scripps Research InstituteThe Skaggs Institute for ChemicalBiology and Department of Chemistry10550 North Torrey Pines RoadLa Jolla, CA 92037USA

Vincenzo BalzaniUniversità di BolognaDipartimento di Chimica“G. Ciamician”Via Selmi 240126 BolognaItaly

Wesley R. BrowneUniversity of GroningenStratingh Institute for Chemistry &Zernike Institute for AdvancedMaterialsFaculty of Mathematics and NaturalSciencesNijenborgh 49747 AG, GroningenThe Netherlands

Alberto CrediUniversità di BolognaDipartimento di Chimica “ G.Ciamician”Via Selmi 240126 BolognaItaly

Johannes A.A.W. ElemansRadboud University NijmegenInstitute for Moleculesand Materials Toernooiveld 16525 ED NijmegenThe Netherlands

Ben L. FeringaUniversity of GroningenStratingh Institute for Chemistry &Zernike Institute for AdvancedMaterialsFaculty of Mathematics and NaturalSciencesNijenborgh 49747 AG GroningenThe Netherlands

Makoto FujitaThe University of TokyoSchool of EngineeringDepartment of Applied Chemistry7-3-1 Hongo, Bunkyo-kuTokyo 113-8656Japan

Pierre GaspardUniversité Libre de BruxellesCenter for Nonlinear Phenomena andComplex SystemsCode Postal 231, Campus Plaine1050 BrusselsBelgium

Kirsten E. GriffithsNorthwestern UniversityDepartment of Chemistry2145 Sheridan RoadEvanston, IL 60208USA

Devens GustArizona State UniversityCenter for Bioenergy andPhotosynthesisDepartment of Chemistry andBiochemistryTempe, AZ 85287USA

Kimoon KimPohang University of Science andTechnologyNational Creative Research InitiativeCenter for Smart Supramolecules andDepartment of ChemistrySan 31 HyojadongPohang 790-784Republic of Korea

Jean-Pierre LaunayCenter for Materials Elaboration andStructural Studies (CEMES)CNRS29 rue Jeanne Marvig31055 Toulouse Cedex 04France

Josef MichlUniversity of ColoradoDepartment of Chemistry andBiochemistryBoulder, CO 80309-0215USAandAcademy of Sciences of the CzechRepublicInstitute of Organic Chemistry andBiochemistryFlemingovo nam. 216610, Prague 6Czech Republic

Ana L. MooreArizona State UniversityCenter for Bioenergy andPhotosynthesisDepartment of Chemistry andBiochemistryTempe, AZ 85287USA

Thomas A. MooreArizona State UniversityCenter for Bioenergy andPhotosynthesisDepartment of Chemistry andBiochemistryTempe, AZ 85287USA

Takashi MuraseThe University of TokyoSchool of EngineeringDepartment of Applied Chemistry7-3-1 Hongo, Bunkyo-kuTokyo 113-8656Japan

Roeland J.M. NolteRadboud University NijmegenInstitute for Molecules and MaterialsToernooiveld 16525 ED NijmegenThe Netherlands

John-Carl OlsenNorthwestern UniversityDepartment of Chemistry2145 Sheridan RoadEvanston, IL 60208USA

Toribio F. OteroUniversidad Politécnica de CartagenaCentre for Electrochemistry andIntelligent Materials30203 CartagenaSpain

Dirk PijperUniversity of GroningenStratingh Institute for Chemistry &Zernike Institute for AdvancedMaterialsFaculty of Mathematics and NaturalSciencesNijenborgh 49747 AG, GroningenThe Netherlands

Michael M. PollardUniversity of GroningenStratingh Institute for Chemistry &Zernike Institute for AdvancedMaterialsFaculty of Mathematics and NaturalSciencesNijenborgh 49747 AG, GroningenThe Netherlands

Jacques ProstPhysicochimie Curie (CNRS-UMR168)Institut Curie, Section de Recherche26 rue d’Ulm75248 Paris Cedex 05FranceandEcole Sup é rieure de Physique et deChimie Industrielles (ESPCI)10 rue Vauquelin75231 Paris Cedex 05France

Julius Rebek Jr.The Scripps Research InstituteThe Skaggs Institute for ChemicalBiology and Department of Chemistry10550 North Torrey Pines RoadLa Jolla, CA 92037USA

David N. ReinhoudtUniversity of TwenteMESA+ Institute for NanotechnologyLaboratory of supramolecularChemistry and TechnologyDrienerlolaan 57522 NB, EnschedeThe Netherlands

Alan E. RowanRadboud University NijmegenInstitute for Molecules and MaterialsToernooiveld 16525 ED NijmegenThe Netherlands

Jeremy K. M. SandersUniversity Chemical LaboratoryDepartmentof ChemistryLensfield RoadCambridge, CB21EW UK

Jean-Pierre SauvageUniversité de StrasbourgInstitut de ChimieLaboratoire de ChimieOrgano-Minérale4, rue Blaise Pascal67070 Strasbourg-CedexFrance

A. Prasanna de SilvaQueen’s UniversitySchool of Chemistry and ChemicalEngineeringBelfast, BT95AG, Northern IrelandUK

J. Fraser StoddartNorthwestern UniversityDepartment of Chemistry2145 Sheridan RoadEvanston, IL 60208USA

Margherita VenturiUniversità di BolognaDipartimento di Chimica “ G.Ciamician”Via Selmi 2, 40126 BolognaItaly

Description

21st Solvay Conference on Chemistry

Hotel Metropole (Brussels), 28 November–1 December 2007

“From Noncovalent Assemblies to Molecular Machines”

Chair: Professor Jean-Pierre Sauvage

The 21st Solvay Conference on Chemistry took place in Brussels between 28 November and 1st December 2007, according to the tradition initiated by Lorentz at the 1st Solvay Conference on Physics in 1911 (“Premier Conseil de Physique Solvay). The Conference was followed on 2nd December by a public event, during which J.-M. Lehn delivered a public lecture entitled “De la Matière à la Vie: la Chimie? La Chimie!” and a panel of scientists (B. Feringa, V. Heitz, J.-P. Launay, J.-M. Lehn, D. Leigh, A. Moore, J.-P. Sauvage and F. Stoddart) answered questions from the audience.

The organization of the 21st Solvay Conference has been made possible thanks to the generous support of the Solvay Family, the Solvay Company, the Belgian National Lottery, the “Université Libre de Bruxelles”, the “Vrije Universiteit Brussel”, the “Communauté française de Belgique”, the David and Alice Van Buuren Foundation, the Wiener Anspach Foundation and the Hotel Metropole.

Opening Session

Opening address by Marc Henneaux

Dear colleagues, dear friends,

In the name of the International Solvay Institutes, it is my great pleasure to welcome all of you to the 21st Solvay Conference on Chemistry. This is the first Solvay Conference on Chemistry to be held in the 21st century.

Since I have only a few minutes, I will be brief. I thought it would be of interest to give you some historical background on the Solvay Conferences on Chemistry.

The history of the International Solvay Institutes started in 1911, with the first Solvay Conference on Physics. I am sure that you have all seen the famous photograph where Marie Curie, Lorentz, Poincar é, the young Einstein and other celebrities surround Ernest Solvay.

In view of the success of the 1911 conference, Ernest Solvay created the Institute of Physics in 1912 and the Institute of Chemistry in 1913, which have now merged into the “International Institutes for Physics and Chemistry, founded by Ernest Solvay”, or the “International Solvay Institutes” for short. One central mission of the Solvay Institutes is periodically to organize the famous Solvay Conferences. The list of all the conferences that have taken place in chemistry is as follows:

1. 1922 Cinq Questions d’ActualitéChair : William Pope (Cambridge)

2. 1925 « Structure et Activité Chimique »Chair : William Pope (Cambridge)

3. 1928 « Questions d’Actualité »Chair : William Pope (Cambridge)

4. 1931 « Constitution et Configuration des Molécules Organiques »Chair : William Pope (Cambridge)

5. 1934 « L’Oxygène, ses réactions chimiques et biologiques »Chair : William Pope (Cambridge)

6. 1937 « Les Vitamines et les Hormones »Chair : Fred Swarts (Gand)

7. 1947 « Les Isotopes »Chair : Paul Karrer (Zurich)

8. 1950 « Le Mécanisme de l’Oxydation »Chair : Paul Karrer (Zurich)

9. 1953 « Les Protéines »Chair : Paul Karrer (Zurich)

10. 1956 « Quelques Problèmes de Chimie Minérale »Chair : Paul Karrer (Zurich)

11. 1959 « Les Nucléoprotéines »Chair : A.R. Ubbelohde (London)

12. 1962 « Transfert d’Energie dans les Gaz »Chair : A.R. Ubbelohde (London)

13. 1965 « Reactivity of the Photoexited Organic Molecule »Chair : A.R. Ubbelohde (London)

14. 1969 « Phase Transitions »Chair : A.R. Ubbelohde (London)

15. 1970 « Electrostatic Interactions and Structure of Water »Chair : A.R. Ubbelohde (London)

16. 1976 « Molecular Movements and Chemical Reactivity as conditioned by Membranes, Enzymes and other Molecules »Chair : A.R. Ubbelohde (London)

17. 1980 « Aspects of Chemical Evolution »Chair : A.R. Ubbelohde (London)

18. 1983 « Design and Synthesis of Organic Molecules Based on Molecular Recognition »Chairs : Ephraim Katchalski (Rehovot) and Vladimir Prelog (Zurich)

19. 1987 « Surface Science »Chair : Frederik W. de Wette (Austin)

20. 1995 « Chemical Reactions and their Control on the Femtosecond Time Scale »Chair : Pierre Gaspard (Brussels)

A striking feature of the subjects of the conferences is their diversity, ranging from physics to biology.

The previous conference on chemistry took place in 1995. With the organization of the 21st Conference, 12 years after the 20th one, we are happy, at the Solvay Institutes, to revive a tradition that has been dormant since then. I would like to express our deepest thanks to the Solvay Scientific Committee for Chemistry, represented here by its Professors Stuart Rice (chair), Graham Fleming, Henk Lekkerkerker, Jean-Marie Lehn and Albert Goldbeter (secretary), who chose the subject of the conference, and to Professor Jean-Pierre Sauvage from the University of Strasbourg who accepted to chair it.

In preparing my speech, I was informed by Professor Franklin Lambert (VUB) that there are, in fact, many historical links between the University of Brussels and the Solvay Institutes on the one hand, and the University of Strasbourg on the other hand. These links go back to the early days of the Institutes, after the First World War. The physicist Pierre Weiss, known for his important work on magnetism, was a cornerstone of this cooperation. It is interesting to note that Pierre Weiss, as early as in 1920, pushed for an exchange program between professors and lecturers of both Brussels and Strasbourg Universities, and even suggested an equivalence of degrees and diplomas … it was the Bologna program before the Bologna program but without the bureaucracy. Pierre Weiss himself came many times to Brussels to give lectures, and received a golden medal from the University.

With the 21st Solvay Conference on Chemistry, we are pleased to renew the tradition of cooperation with Strasbourg. I wish you a very fruitful meeting, and I am very happy to give the floor to Jean-Pierre Sauvage.

The International Solvay Institutes

Board of DirectorsMembersMr Solvay†PresidentProfessor Franz BingenEmeritus–Professor VUBVice-President and TreasurerProfessor Rosette S’JegersVice-rector VUB and Professor VUBSecretaryProfessor Françoise Thys-ClémentHonorary Rector and Professor ULBMr Philippe BusquinEuropean Deputy and Former European CommmissionerBaron Daniel JanssenHonorary Chairman of the Board of Directors of Solvay S.A.Mr Jean-Marie SolvayMember of the Board of Directors of Solvay S.A.Mr Eddy Van GelderPresident of the Administrative Board of the VUBProfessor Jean-Louis VanherweghemPresident of the Administrative Board of the ULBHonorary MembersProfessor Irina VeretennicoffProfessor VUBBaron JaumotteHonorary Rector and Honorary President ULBHonorary Director

Mr Jean-Marie PiretAttorney General of the Supreme Court of Appeal and Honorary Principal PrivateSecretary to the King

GuestsProfessor Marc HenneauxProfessor ULBDirectorProfessor Franklin LambertProfessor VUBDeputy DirectorProfessor Albert GoldbeterProfessor ULBScientific Secretary of the Committee for ChemistryProfessor Alexandre SevrinProfessor VUBScientific Secretary of the Committee for PhysicsMr Pascal De WitAdviser Solvay S.A.Professor Niceas SchampSecretary of the Royal Flemish Academy forSciences and Arts

† Deceased April 29, 2010.

Solvay Scientific Committee for Chemistry

ChairProfessor Stuart Rice, University of Chicago, USA

MembersProfessor Manfred EigenMax-Planck Institut, Göttingen, Germany

Professor Graham FlemingUniversity of Berkeley, USA

Professor Harold W. KrotoUniversity of Sussex, Brighton, UK

Professor Jean-Marie LehnCollège de France, Paris, France

Professor Henk N.W. LekkerkerkerUtrecht Universiteit, the Netherlands

Professor Mario J. MolinaMassachusetts Institute of Technology, Cambridge, USA

Professor K.C. NicolaouUniversity of California, San Diego, USA

Professor Kurt WüthrichInstitut Fédéral Suisse de Technologie, Zurich, Switzerland

Scientific SecretaryProfessor Albert GoldbeterUniversité Libre de Bruxelles, Belgium

21st Solvay Conference on Chemistry

ParticipantsTakuzoAidaUniversity of Tokyo, JapanHarryAndersonUniversity of Oxford, UKR. DeanAstumianUniversity of Maine, USAVincenzoBalzaniUniversità di Bologna, ItalyPaulBeerUniversity of Oxford, UKAlbert M.BrouwerUniversity of Amsterdam, The NetherlandsAlbertoCrediUniversità di Bologna, ItalyEnricoDalcanaleUniversità di Parma, ItalyA. Prasannade SilvaQueen’s University Belfast, UKLuigiFabbrizziUniversità di Pavia, ItalyBen L.FeringaUniversity of Groningen, The NetherlandsGrahamFlemingUniversity of California Berkeley, USAMakotoFujitaUniversity of Tokyo, JapanDevensGustArizona State University, USAAkiraHaradaOsaka University, JapanValérieHeitzUniversité de Strasbourg, FranceChristopherHunterUniversity of Sheffield, UKChristianJoachimCEMES-CNRS, FranceKimoonKimPohang University of Sciences and Technology, KoreaJean-PierreLaunayCEMES-CNRS, FranceJean-MarieLehnUniversité de Strasbourg, FranceDavid A.LeighUniversity of Edinburgh, UKHenkLekkerkerkerUtrecht University, The NetherlandsJosefMichlUniversity of Colorado, USAAna L.MooreArizona University, USAThomas A.MooreArizona University, USARoelandNolteUniversity of Nijmegen, The NetherlandsToriobio F.OteroUniversidad Politécnica de Cartagena, SpainJacquesProstEcole Supérieure de Physique et de Chimie Industrielles (ESPCI)KennethRaymondUniversity of California, USAJuliusRebekThe Skaggs Institute for Chemical Biology, USADavid N.ReinhoudtUniversity of Twente, The NetherlandsStuartRiceUniversity of Chicago, USARolf W.SaalfrankUniversität Erlangen-Nürnberg, GermanyJeremy K. M.SandersUniversity of Cambridge, UKJean-PierreSauvageUniversité de Strasbourg, FranceChristoph A.SchalleyFreie Univesität Berlin, GermanyAbrahamShanzerWeizmann Institute of Sciences, IsraelSeijiShinkaiKyushu University, JapanMitsuhikoShionoyaThe University of Tokyo, JapanJ. FraserStoddartUniversity of California, USAFritzVögtleUniversität Bonn, GermanyKrzysztofWozniakWarsaw University, PolandAuditorsKristinBartikULBDavideBonifaziFUNDPStevenDe FeyterKULeuvenStéphanieDurotStrasbourgPierreGaspardULBPaulGeerlingsVUBYvesGeertsULBJohanHofkensKULeuvenIvanJabinULBAlainJonasUCLFannyKirschULBRenéLefeverULBPaulMandelULBJoseMartinsGhentCécileMoucheronULBJacquesReisseULBChristianVen den BroeckHasseltStéphaneVincentFUNDPScientific Secretary of the ConferenceKritstinBartikULBStéphanieDurotStrasbourgYvesGeertsULBIvanJabinULBFannyKirschULBCécileMoucheronULBSergeySergeyevULBAdministrative Secretary of theConferenceDominiqueBogaertsSolvay InstitutesIsabelleJuifSolvay Institutes

Part One

Noncovalent Assemblies: Design and Synthesis

1

Introduction and Definition of Noncovalent Assemblies

Julius Rebek Jr

It is my very pleasant duty as Session Chairman to open this Solvay Conference on Chemistry and welcome you, the participants, to “Noncovalent Assemblies.” It is not a very pleasant a duty to define this field–after all, every crystal is a self-assembly, every monolayer, membrane, vesicle and micelle is a self-assembly, and every metal – ligand interaction is also a self-assembly. In fact, at some level, every synthesis is a self-assembly. But, unfortunately, as we cannot include them all, some must be excluded. As there is no graceful way to do this, I will define our work this morning arbitrarily as “finite systems that persist in solution.” Yet, even that term is unsatisfactory –although crystalline urea-based inclusion compounds and cholic acid complexes have been known for decades, they must persist at some level in solution, even though we are not yet able to analyze them on the timescales and instrumentation available today. Likewise, in this morning’s presentations we can exclude zeolites and the newer Metal Organic Frameworks, even though they demonstrate enviable functions in the solid state. I mention this in an attempt to focus and stimulate discussion on those noncovalent assemblies that do show function. The early solution assemblies which used metal – ligand interactions or hydrogen bonds had no apparent function –they merely filled space (Figure 1.1).

But, we shall see that function arises from the proper filling of space: we all know that Nature abhors a vacuum, and a price must be paid to create one. Nonetheless, there are rewards waiting for those can who manipulate molecules into fixed spaces. Today, I have invited those who have taken these enormous steps, and many strides beyond the Werner coordination complexes, such that a century later we are aiming at different targets (see Figure 1.2). Parallel developments with hydrogen-bonded systems also moved the focus from space filling to function; indeed, the melamine/cyanuric acid pattern was tailored for finite assemblies (see Figure 1.3): and also for rosettes (Figure 1.4): while recent activity in the cucurbiturils also warrants discussion (Figure 1.5):

Figure 1.1 Upper section. Left: A catenane self-assembled by Sauvage and coworkers [1], using Cu as a template; Right: A schematic cartoon of a helicate with two Zn metals, as devised by Fuhrhop and colleagues [2] in 1976. Lower section. The self-sorting series of helicates as created by Lehn and Rigault [3], in 1988.

Figure 1.2 Left: Raymond et al.’s [4] capsule represented schematically. A phosphine/ acetone adduct was stabilized inside and isolated from the bulk solvent. More recently, iminimum ion-reactive intermediates have been stabilized in the same capsule. Right: A cartoon of Fujita and colleagues ’ [5] “ship-in-a-bottle”-type synthesis of a silanol inside a capsule. Neither encapsulated product is stable outside the capsule.

Figure 1.3 The melamine/cyanuric acid hydrogen-bonding recognition pattern as adopted by Seto and Whitesides [6], which creates a 3 : 1 assembly.

Figure 1.4 The melamine/cyanuric acid pattern presented on calixarene platforms as a rosette discovered by Reinhoudt and coworkers [7], that has encapsulation properties.

Figure 1.5 Two guests encapsulated in a cucurbit[10]uril by Isaacs et al . [8] (left), and an inverted version by Kim, Isaacs and colleagues [9] (right).

The good news is that I have invited some of the research workers featured above –including Ken Raymond, Kimoon Kim and David Reinhoudt–to highlight their investigations and to stimulate the discussion that will be held during the second half of this session, on noncovalent assemblies.

For now, among those who have been invited, the first to report their findings will be Makoto Fujita. So, without any further introduction, let me turn things over to Makoto – if you don’t know who he is, then you have wandered into the wrong hotel room! So, fasten your seatbelts and turn off your cellphones!

References

1 Dietrich-Buchecker, C.O., Sauvage, J.-P., and Kern, J.-M. (1984) J. Am. Chem. Soc., 106, 3043–3045.

2 Struckmeier, G., Thewalt, U., and Fuhrhop, J.H. (1976) J. Am. Chem. Soc., 98, 278.

3 Lehn, J.-M. and Rigault, A. (1988) Angew. Chem., 100, 1121.

4 Dong, V.M., Fiedler, D., Carl, B., Bergman, R.G., and Raymond, K.N. (2006) J. Am. Chem. Soc., 128, 14464.

5 Yoshizawa, M., Kuskawa, T., Fujita, M., and Yamaguchi, K. (2000) J. Am. Chem. Soc., 122, 6311–6312.

6 (a) Seto, C.T. and Whitesides, G.M. (1990) J. Am. Chem. Soc., 112, 6409. (b) J.P. Mathias, E.E. Simanek, C.T. Seto, G.M. Whitesides, Angew. Chem., 1993, 105, 1848–1850.

7 Kerckhoffs, J.M.C.A., ten Cate, M.G.J., Mateos-Timoneda, M.A., van Leeuwen, F.W.B., Snellink-Ruël, B., Spek, A.L., Kooijman, H., Crego-Calama, M., and Reinhoudt, D.N. (2005) J. Am. Chem. Soc., 127, 12697–12708.

8 Huang, W.-H., Liu, S., Zavalij, P.Y., and Isaacs, L. (2005) J. Am. Chem. Soc., 127, 16798–16799.

9 Isaacs, L., Park, S.-K., Liu, S., Ko, Y.H., Selvapalam, N., Kim, Y., Kim, H., Zavalij, P.Y., Kim, G.-H., Lee, H.-S., and Kim, K. (2005) J. Am. Chem. Soc., 127, 18000–18001.