Supramolecular Chemistry of Fullerenes and Carbon Nanotubes E-Book

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

Seitenzahl: 700

Veröffentlichungsjahr: 2012

Beschreibung

Collating our current knowledge and the latest developments for enabling breakthrough discoveries, this book focuses on the synthesis and applications of materials that are based on supramolecular assemblies of carbon nanostructures, with an emphasis on fullerenes and nanotubes. In so doing, it provides readers with an overview of the different types of supramolecular architectures, accentuating the outstanding geometrical, electronic and photophysical properties of the building blocks and the resulting structures. It makes use of basic concepts and real-life applications -- from simple syntheses to complex architectures, from instructive examples to working experimental procedures, and from photophysics to solar cells. A large part of each chapter is devoted to the methods and possibilities of controlling and tuning these molecular assemblies in order to obtain working devices. Fascinating reading for materials scientists, organic chemists, molecular physicists, and those in the semiconductor industry.

Leseprobe

Contents

Cover

Related Titles

Title Page

Copyright

Preface

List of Contributors

Chapter 1: Carbon Nanostructures: Covalent and Macromolecular Chemistry

1.1 Introduction

1.2 Fullerene-Containing Polymers

1.3 Carbon Nanotubes

1.4 Graphenes

1.5 Summary and Conclusions

Acknowledgments

References

Chapter 2: Hydrogen-Bonded Fullerene Assemblies

2.1 Introduction

2.2 Hydrogen-Bonded Fullerene-Based Supramolecular Structures

2.3 Hydrogen-Bonded Fullerene-Based Donor–Acceptor Structures

2.4 Applications

Acknowledgments

References

Chapter 3: Receptors for Pristine Fullerenes Based on Concave–Convex π–π Interactions

3.1 Introduction

3.2 Fullerene Receptors Based on Traditional Hosts

3.3 Hydrocarbon Receptors

3.4 Receptors Bearing a Curved Conjugated System

3.5 Conclusions

References

Chapter 4: Cooperative Effects in the Self-Assembly of Fullerene Donor Ensembles

4.1 Introduction

4.2 Allosteric Cooperativity

4.3 Chelate Cooperativity

4.4 Conclusions

4.5 Experimental Details

Acknowledgments

References

Chapter 5: Fullerene-Containing Rotaxanes and Catenanes

5.1 Introduction

5.2 Fullerene Rotaxanes and Catenanes

5.3 Conclusions

References

Chapter 6: Biomimetic Motifs Toward the Construction of Artificial Reaction Centers

6.1 Introduction

6.2 Supramolecular Architectures for Solar Energy Conversion

6.3 Outlook

References

Chapter 7: Supramolecular Chemistry of Fullerene-Containing Micelles and Gels

7.1 Introduction

7.2 Solubilization of Pristine C60 in Surfactant Assemblies

7.3 Self-Assemblies of Amphiphilic C60 Derivatives

7.4 Gels of Fullerenes

7.5 Conclusions and Outlook

References

Chapter 8: Fullerene-Containing Supramolecular Polymers and Dendrimers

8.1 Introduction

8.2 Fabrication of [60]Fullerene Polymeric Array

8.3 Supramolecular Polymerization of Functionalized [60]Fullerene

8.4 Supramolecular [60]Fullerene Dendrimer

8.5 Conclusions

References

Chapter 9: [60]Fullerene-Containing Thermotropic Liquid Crystals

9.1 Introduction

9.2 Noncovalent C60 Derivatives

9.3 Covalent C60 Derivatives

9.4 Conclusions

Acknowledgments

References

Chapter 10: Supramolecular Chemistry of Fullerenes on Solid Surfaces

10.1 Introduction

10.2 Fullerenes on Nonpatterned Metal Surfaces

10.3 Surface Templates for Fullerene Adsorption

10.4 Supramolecular Aggregation of Fullerenes and other Organic Species on Surfaces

10.5 Outlook

Acknowledgments

References

Chapter 11: Supramolecular Chemistry of Carbon Nanotubes

11.1 Introduction

11.2 Supramolecular Carbon Nanotube Hybrids

11.3 Conclusions

References

Chapter 12: Supramolecular Chemistry of Fullerenes and Carbon Nanotubes at Interfaces: Toward Applications

12.1 Introduction

12.2 Fullerene Interfaces

12.3 Carbon Nanotubes

12.4 Conclusions

References

Chapter 13: Applications of Supramolecular Ensembles with Fullerenes and CNTs: Solar Cells and Transistors

13.1 Introduction

13.2 Solar Cells

13.3 Transistors

13.4 Summary

References

Chapter 14: Experimental Determination of Association Constants Involving Fullerenes

14.1 Planning a Titration Experiment

14.2 Performing a Titration

14.3 Choosing the Spectroscopic Method

14.4 Analyzing the Data

14.5 Determining Stoichiometry

14.6 Estimating Errors

14.7 Fullerenes as Guests: Spectroscopic Properties

14.8 Determination of the Binding Constant of an exTTF-based Host toward C60: A Practical Example

14.9 Conclusions

References

Index

Related Titles

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Guldi, D. M., Martín, N. (eds.)Carbon Nanotubes and Related Structures Synthesis, Characterization, Functionalization, and Applications 2010 ISBN: 978-3-527-32406-4

Martín, N., Giacalone, F. (eds.)Fullerene Polymers Synthesis, Properties and Applications 2009 ISBN: 978-3-527-32282-4

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Preface

Three great scientists, Jean-Marie Lehn, Donald J. Cram, and Charles J. Pedersen, received the Nobel Prize in Chemistry in 1987 for the development and utilization of molecules with highly selective structure-specific interactions. Only 2 years before, in 1985, fullerenes were discovered and, in 1996, Sir Harold W. Kroto, Robert F. Curl, and the late Richard E. Smalley were awarded the Nobel Prize in Chemistry for the discovery of these new carbon allotropes. Soon after this seminal finding, the discovery of multi- and single-wall carbon nanotubes (CNTs) in 1991 and 1993, respectively, provided a new kind of carbon allotropes with cylindrical geometry that belong structurally to the family of fullerenes. Although both areas of chemistry (supramolecular chemistry and fullerenes) have been thoroughly studied in the past two decades and very significant advances in terms of basic knowledge and practical applications have independently been made, more recently they gave rise to a new interdisciplinary field in which the imagination of chemists has afforded unprecedented fullerene-based supramolecular architectures.

This year we celebrate the 25th anniversary of the awarding of Nobel to those scientists who brought to the attention of the scientific community the new concept of supramolecular chemistry. Therefore, it is an excellent opportunity to comment on the most important achievements and future goals in this emerging field of supramolecular chemistry of fullerenes and carbon nanotubes.

The huge number of publications during the past decade devoted to fullerenes and supamolecular chemistry attest the interest in this new avenue of chemistry stemming from both fields. The use of concepts and principles of supramolecular chemistry to fullerenes and carbon nanotubes has reached an outstanding position in its own right and we certainly believe that it constitutes a new interdisciplinary field with basic research interest and important potential applications in fields such as biomedical and materials sciences.

Therefore, in this timely book containing 14 chapters, we have gathered the most important developments authored by leading scientists actively engaged in supramolecular/fullerene research, thus giving a precise picture on the state of the art in this new hybrid field.

One of the major challenges nowadays in chemistry is the control of weak forces, on a molecular basis, which will eventually lead to the definition of the size and shape in relation to function of the resulting supramolecular ensembles. In this regard, the rigid structure and round and rod shape of fullerenes and CNTs, respectively, as well as their remarkable electronic properties result in rather unique scaffolds for the development of unprecedented carbon-based nanoarchitectures. For these purposes, the different types of weak forces, namely, hydrogen bonding, π–π stacking, coordination of metal cations, electrostatic interactions, and solvophobic forces have been used in the different chapters to construct new noncovalently bonded structures. A singular aspect in the construction of new architectures involving these weak forces is that, in contrast to covalently bonded structures, they are reversible and their binding energies can be tailored “at will” by means of the chemical environment and temperature.

The book starts with the first chapter devoted to the general introduction to the field of fullerenes and CNTs emphasizing the main achievements in covalent and macromolecular chemistry. The following chapters are devoted to the main supramolecular topics such as H-bonded fullerene assemblies, receptors for pristine fullerenes based on concave–convex π–π interactions, cooperative effects on the self-assembly of fullerene–donor ensembles, fullerene-containing catenanes and rotaxanes, biomimetic motifs toward the construction of artificial reaction centers, supramolecular chemistry of fullerene-containing micelles and gels, fullerene-containing supramolecular polymers and dendrimers, fullerene-containing thermotropic liquid crystals, organizing fullerenes on solid surfaces with STM, supramolecular chemistry of fullerenes and carbon nanotubes at interfaces: toward the application of supramolecular ensembles with fullerenes and CNTs, solar cells and transistors, and supramolecular chemistry of carbon nanotubes. The last chapter is dedicated to the experimental determination of association constants involving fullerenes.

The guest editors want to express their gratitude to the many authors who have participated in this venture for their efforts to bring out this outstanding and unique book in which, for the first time, the supramolecular chemistry of the important carbon allotropes, fullerenes and CNTs, are brought together for the benefit of the reader.

We hope that this book on this new interdisciplinary field be a stimulus for young researchers and would put a new heart into other colleagues to develop new chemical concepts and molecular architectures in which imagination would be the only limitation.

Nazario Martín and Jean-François Nierengarten, editors

List of Contributors

Davide Bonifazi University of Namur (FUNDP) Department of Chemistry Rue Bruxelles 61 5000 Namur Belgium University of Trieste Department of Chemical and Pharmaceutical Sciences Piazzale Europa 1 34127 Trieste Italy

Stéphane Campidelli CEA, IRAMIS Laboratoire d'Electronique Moléculaire CEA Saclay 91191 Gif sur Yvette Cedex France

Robert Deschenaux Université de Neuchâtel Institut de Chimie Laboratoire de Chimie Macromoléculaire Avenue de Bellevaux 51 2000 Neuchâtel Switzerland

Bertrand Donnio Université de Strasbourg UMR 7504 CNRS Institut de Physique et Chimie des Matériaux de Strasbourg 23 Rue du Loess, BP43 67034 Strasbourg Cedex 2 France

Arianna Filoramo CEA, IRAMIS Laboratoire d'Electronique Moléculaire CEA Saclay 91191 Gif sur Yvette Cedex France

José María Gallego Instituto Madrileño de Estudios Avanzados en Nanociencia (IMDEA-Nanociencia) Cantoblanco 28049 Madrid Spain Consejo Superior de Investigaciones Científicas Instituto de Ciencia de Materiales de Madrid Cantoblanco 28049 Madrid Spain

Francesco Giacalone Università di Palermo Department of Organic Chemistry “E. Paternò” 90128 Palermo Italy

Davide Giust University of Castilla la Mancha Department of Organic Inorganic and Biochemistry Av. da José Cela 10 13071 Ciudad Real Spain

Bruno Grimm Friedrich-Alexander-Universitaet Erlangen-Nuermberg Interdisciplinary Center for Molecular Materials (ICMM) Department of Chemistry and Pharmacy Egerlandstr. 3 91058 Erlangen Germany

Daniel Guillon Université de Strasbourg UMR 7504 CNRS Institut de Physique et Chimie des Matériaux de Strasbourg 23 Rue du Loess, BP43 67034 Strasbourg Cedex 2 France

Dirk M. Guldi Friedrich-Alexander-Universitaet Erlangen-Nuermberg Interdisciplinary Center for Molecular Materials (ICMM) Department of Chemistry and Pharmacy Egerlandstr. 3 91058 Erlangen Germany

Takeharu Haino Hiroshima University Graduate School of Science Department of Chemistry 1-3-1 Kagamiyama Higashi-Hiroshima City 739-8526 Japan

Ma Ángeles Herranz Universidad Complutense de Madrid Facultad de Ciencias Químicas Departamento de Química Orgánica 28040 Madrid Spain

Toshiaki Ikeda Hiroshima University Graduate School of Science Department of Chemistry 1-3-1 Kagamiyama Higashi-Hiroshima City 739-8526 Japan

Beatriz M. Illescas Universidad Complutense de Madrid Facultad de Ciencias Químicas Departamento de Química Orgánica 28040 Madrid Spain

Hiroshi Imahori Kyoto University Institute for Integrated Cell-Material Sciences (iCeMS) Kyotodaigaku-katsura Nishikyo-ku Kyoto 615-8501 Japan Kyoto University Graduate School of Engineering Department of Molecular Engineering Nishikyo-ku Kyoto 615-8501 Japan

Bruno Jousselme CEA, IRAMIS Laboratoire de Chimie des Surfaces et Interfaces CEA Saclay 91191 Gif sur Yvette Cedex France

Takeshi Kawase University of Hyogo Graduate School of Engineering Department of Materials Science and Chemistry Shosha 2167 Himeji Hyogo 671-2280 Japan

Adrian Kremer University of Namur (FUNDP) Department of Chemistry Rue Bruxelles 61 5000 Namur Belgium

Hongguang Li Max Planck Institute of Colloids and Interfaces Department of Interfaces MPI-NIMS International Joint Laboratory Am Mühlenberg 1 14476 Potsdam Germany

Riccardo Marega University of Namur (FUNDP) Department of Chemistry Rue Bruxelles 61 5000 Namur Belgium

Nazario Martín Universidad Complutense de Madrid Facultad de Ciencias Químicas Departamento de Química Orgánica 28040 Madrid Spain Universidad Autónoma de Madrid Facultad de Ciencias IMDEA-Nanociencia Ciudad Universitaria de Cantoblanco Módulo C-IX, 3a Planta 28049 Madrid Spain

Aurelio Mateo-Alonso Albert-Ludwigs-Universität Freiburg Freiburg Institute for Advanced Studies (FRIAS) School of Soft Matter Research Albertstrasse 19 79104 Freiburg im Breisgau Germany Albert-Ludwigs-Universität Freiburg Institut für Organische Chemie und Biochemie Albertstrasse 21 79104 Freiburg im Breisgau Germany

Rodolfo Miranda Universidad Autónoma de Madrid Departamento de Física de la Materia Condensada Cantoblanco 28049 Madrid Spain Instituto Madrileño de Estudios Avanzados en Nanociencia (IMDEA-Nanociencia) Cantoblanco 28049 Madrid Spain

Takashi Nakanishi National Institute for Materials Science (NIMS) Organic Materials Group 1-2-1 Sengen Tsukuba 305-0047 Japan

Jean-François Nierengarten Université Louis Pasteur et CNRS (UMR 7509) Ecole Européenne de Chimie Polymères et Matériaux (ECPM) Laboratoire de Chimie des Matériaux Moléculaires 25 rue Becquerel 67087 Strasbourg Cedex 2 France

Roberto Otero Universidad Autónoma de Madrid Departamento de Física de la Materia Condensada Cantoblanco 28049 Madrid Spain Instituto Madrileño de Estudios Avanzados en Nanociencia (IMDEA-Nanociencia) Cantoblanco 28049 Madrid Spain

Emilio M. Pérez IMDEA Nanociencia Campus Universitario de Cantoblanco Facultad de Ciencias Módulo C-IX, 3a planta 28049 Madrid Spain

Luis Sánchez Universidad Complutense de Madrid Facultad de Ciencias Químicas Departamento de Química Orgánica 28040 Madrid Spain

Sukumaran Santhosh Babu National Institute for Materials Science (NIMS) Organic Materials Group 1-2-1 Sengen Tsukuba 305-0047 Japan Max Planck Institute of Colloids and Interfaces Department of Interfaces MPI-NIMS International Joint Laboratory Am Mühlenberg 1 14476 Potsdam Germany

José Santos Universidad Complutense de Madrid Facultad de Ciencias Químicas Departamento de Química Orgánica 28040 Madrid Spain

Tomokazu Umeyama Kyoto University Graduate School of Engineering Department of Molecular Engineering Nishikyo-ku Kyoto 615-8501 Japan

Chapter 1

Carbon Nanostructures: Covalent and Macromolecular Chemistry

Francesco Giacalone, Maa Ángeles Herranz, and Nazario Martín

1.1 Introduction

The aim of this introductory chapter is to bring to the attention of the readers the achievements made in the chemistry of carbon nanostructures and, mostly, in the chemistry of fullerenes, carbon nanotubes (CNTs), and the most recent graphenes. Since the discovery of fullerenes in 1985 and their further preparation in multigram amounts, the chemistry and reactivity of these molecular carbon allotropes have been well established. Actually, this chemical reactivity has been used as a benchmark for further studies carried out in the coming carbon nanotubes (single and multiple wall) and graphenes. Assuming that the fundamental chemistry of fullerenes is known and basically corresponds to that of typical electron-deficient alkenes, we have mainly focused on the chemistry of fullerene-containing polymers. In this regard, the combination of the unique fullerenes with the highly versatile polymer chemistry has afforded a new and interdisciplinary field in which the resulting architectures are able to exhibit unprecedented properties. The basic knowledge of this important topic of macromolecular chemistry of fullerenes nicely complements the following chapters devoted to their supramolecular chemistry.

The chemistry of CNTs, on the other hand, is considerable less developed than that of fullerenes, and most of their studied reactions are generally based on those previously studied on fullerenes. Therefore, despite the recent reviews and books published on CNTs, we feel that an introductory chapter describing the most significant solubilization/derivatization covalent and noncovalent methods should be helpful and welcome by the readers, and particularly to those nonexperts in the field. This same objective has been pursued for the most recent and planar graphenes. The available literature on the chemistry of these one-atom thickness carbon allotropes is considerably less developed. Therefore, some useful chemical procedures reported so far for the functionalization and solubilization of graphenes – thus allowing its manipulation and application for the construction of devices – have also been included at the end of the chapter.

1.2 Fullerene-Containing Polymers

Since the achievement of [60]fullerenes in ponderable amounts [1], its combination with macromolecular chemistry provided an opportunity to generate new fullerene-containing polymers, with potential for a broad scope of real applications since it merges C60 properties with the ease and versatile processability and handling of polymers. This approach prompted chemists to design and develop synthetic strategies aimed to obtain even more complex and fascinating novel fullerene-based architectures with unprecedented properties that have been recently reviewed 2. In fact, chemists are now able to tailor at will a polymeric backbone possessing C60 moieties in such way as to achieve peculiar properties of the final macromolecular material. In this way, block copolymer with well-defined donor–acceptor domains within the diffusion path of electron are created for solar devices [3], or water-soluble biocompatible and biodegradable polymers are designed in order to carry fullerene in circulation for photodynamic cancer therapy purposes 4. These recent achievements are only the tip of the iceberg of a growing field in which almost all the materials display outstanding properties such as optical limiting [5], or photoinduced electron transfer [6] just to name a few. In addition, polyfullerenes have been successfully employed as active materials not only in electroluminescent devices 7 but also in nonvolatile flash devices [8], and in membranes both for gas separation 9 and for proton exchange fuel cells [10].

The many types of polymeric fullerene derivatives may be classified according to their structural features. As a criterion for the classification, polyfullerenes can be ordered as a function of their increasing chemical complexity and the difficulty to synthesize them, and other interesting classes of nondiscrete multifullerene-containing hybrid materials may also be included in this classification (Figure 1.1).

Figure 1.1 Classification of the different types of C60-containing polymers and C60-hybrid materials.

All-fullerene polymers are specifically those materials or structures that are constituted exclusively by fullerene units covalently linked to each other 10. These “intrinsic polymers” are prepared simply by exposing pure fullerene to visible light [12], high pressure [13], electron beam [14], and plasma irradiation 15 without control or care for the final structure. Recently, it has been shown that unbound and bound states of C60 molecules can be reversibly controlled at the single-molecule level in ultrathin films of all-C60 polymers using a tip of a scanning tunneling microscope at RT, thus allowing single-molecule-level topochemical digital data [16].

Heteroatom-containing polymers have metals or elements other than carbon inserted in between two C60 moieties. In 1994, Forró discovered that the fulleride phases AC60 (A: K, Rb, Rb or Cs), undergo [2 + 2] cycloadditions producing polyfullerenes with alkali metals in the crystal voids 17. For the organometallic polymers, the metal doping of C leads to the formation of the corresponding charge transfer polymer [18]. Several different metals have been employed in the polymerization with fullerenes, but among them palladium led to the most promising copolymers with outstanding properties [19]. In fact, the polymer (CPd) has been able to catalyze heterogeneous hydrogenation reactions of alkenes [20]. Very recently, 1D “zigzag” polymers have been achieved by mixing fullerene with the oxidizing superacid AsF [21]. As a result, a polyfullerenium salt in the solid state has been prepared, with C units connected by an alternating sequence of four-membered carbon rings ([2 + 2] cycloaddition) and single C−C bonds stabilized by ASF anions in the lattice.