Nanocarbon chemistry and physics is a fast-developing, broad research area – the Nobel prizes in 1996 and 2010 awarded to two key discoveries in the field, and several other nanocarbon achievements of comparable importance. Owing to this rapid growth, the nanocarbon landscape fundamentally changes every few years, creating a need to survey the field on a regular basis to update the books that have become incomplete or even obsolete. As such, this book focuses on fullerenes and metallofullerenes and also on the related areas of nanotubes and graphenes.
All the covered research topics provide important fundamental knowledge for the natural sciences, but also for applications in molecular electronics, superconductivity, catalysis, photovoltaics and medical diagnostics. The current nanocarbon research activities have particularly high application potential in the conversion of solar energy, future molecular memories, non-conventional materials for optoelectronics, and new treatments for civilization diseases. Offering a truly up-to-date critical survey of nanocarbon science, its concepts and highlights, it follows the concept of a handbook: it addresses key topics systematically, from historical background, methodological aspects, current important issues, and application potential, all supplied with extensive referencing. With individual chapters written by leading experts with extensive research experience, it is a comprehensive reference resource for graduate students and active researchers alike.
Author(s): Xing Lu, Takeshi Akasaka, Zdeněk Slanina
Series: Springer Nature Reference
Publisher: Springer
Year: 2022
Language: English
Pages: 1028
City: Singapore
Preface
Contents
About the Editors
Contributors
Part I: History and Nomenclature of Fullerenes
1 Our Road to Fullerenes: A Personal Account
Introduction
Donald Huffman in Heidelberg
C60 Buckminsterfullerene
Fullerite
A New Form of Solid Carbon
Epilogue
References
Part II: Molecular Structures of Fullerenes
2 Preparation, Extraction/Isolation from Soot, and Solubility of Fullerenes
Introduction
Discussion
Preparation Methods for Fullerenes/Metallofullerenes
Laser Synthesis
Electric Arc-Synthesis
Solar Power
Combustion and Flame Method
Radio-Frequency (RF) Furnace
Extraction and Isolation of Fullerene/Metallofullerenes from Soot
Selective Solubility
Solvent-Free Extraction
Electrochemical Extraction
Chemical Stabilization
Host-Guest Complexation and Extraction
Solubility Studies
Solubility Measurements
Purification of Fullerenes Using Selective Solubility
Concluding Remarks
Cross-References
References
3 Total Synthesis of C60
Introduction
Approaches by Carbon Cage Synthesis
Bottom-Up Synthesis Approach from Buckybowls
Synthesis of Corannulene (22)
Derivatization of Corannulene
Synthesis of Sumanene (23)
Derivatization of Sumanene
FVP Approach
Synthesis on Metal Surfaces
Summary
References
4 Structural Characteristics of Fullerenes
Introduction
Structure Generation
Fullerene Dual
Cage Symmetry
Structural Stability
Naming Schemes
Cage Isomerization and Interconversion
Electronic Structure and Aromaticity
Structural Characterization
Fullerene Derivatization
Nonclassical Fullerenes
Example Structures of Fullerenes
Conclusions
Cross-References
References
5 Theoretical Predictions of Fullerene Stabilities
Introduction
Energetics and Thermodynamics of Nanocarbons
The Relative Populations of Isomeric Nanocarbons
The Relative Stabilities of Nonisomeric Nanocarbons
Enumeration of Fullerene Cages
Relative Populations of Isomeric Empty Fullerenes
Stabilities of Metallofullerenes
Relative Populations of Isomeric Metallofullerenes
Relative Stabilities of Nonisomeric Metallofullerenes
Stabilities of Nonmetal Endohedrals
Stabilities of Clusterfullerenes
Stabilities of Nanocarbon Derivatives
Kinetic Control
Conclusions
Cross-References
References
6 Fullerenes Violating the Isolated Pentagon Rule
Introduction
Nomenclature of Fullerene Carbon Cages
Endohedral Stabilization of Non-IPR Fullerenes
Exohedral Stabilization of Non-IPR Fullerenes
Structures of Synthesized Non-IPR Fullerenes
Conclusion and Outlook
Cross-References
References
7 Merging Carbon Nanostructures with Porphyrins
Introduction
Amorphous Carbon Structures
Carbon Nanodots (CNDs)
Covalent Porphyrin Conjugates
Non-covalent Porphyrin Systems
Crystalline Carbon Structures
Fullerenes
Covalent Porphyrin Conjugates
Non-covalent Porphyrin Systems
Endohedral (Metallo)fullerenes
Covalent Porphyrin Conjugates
Non-covalent Porphyrins
Single-Walled Carbon Nanotubes (SWCNTs)
Covalent Porphyrin Conjugates
Non-covalent Porphyrin Systems
Conclusions
References
8 Connecting Fullerenes with Carbon Nanotubes and Graphene
Introduction
Fullerenes and Carbon Nanotubes
Fullerenes and Graphene: Structural Transformation Mechanism
References
Part III: Chemical Properties of Fullerenes and Metallofullerenes
9 Chemical Reactivity and Addition Pattern on C60 and C70
Introduction
Chemical Modification of Fullerenes
Exohedral Modification
Monoaddition Reactions
Cycloadditions
Radical Additions
Nucleophilic Additions
Dimerization Reactions
Transition-Metal-Catalyzed/Promoted Reactions
Aldehyde/Amine-Participated Reactions
Asymmetric Synthesis
Retro-Cycloaddition Reactions
Mechanochemical Reactions
Multiaddition Reactions
Halogenation
Hydrogenation
Hydroxylation
Additions of Organocopper Reagents
Additions of Peroxides
Additions of Amines
Tether-Directed Remote Functionalization
Skeletal Modification
Formation of Open-Cage Fullerenes
Formation of Heterofullerenes
Concluding Remarks
References
10 Functionalization of Fullerenes: Addition Reactions
Introduction
Addition Reactions
Nucleophilic Additions
Electrophilic Additions
Addition-Elimination Reactions
Carbene and Silylene Additions
1,3-Dipolar Cycloadditions
Nitrene Additions
Phosphine-Mediated Reactions
[2 + 2] Cycloadditions
Diels-Alder Reactions
Cross-References
References
11 Radical Reaction and Photoreaction
Introduction
Equilibrium Reaction of Alkylated C60 Radicals and Their Dimers
Radical Reaction of C60 with Azo(bisisobutyronitrile) (AIBN)
Radical Reaction of C60 with the Perfluoroalkyl Radical
Radical Reaction of C60 with Arylhydrazine
Radical Addition of C60 with (2,2,6,6-Tetramethylpiperidinyl-1-oxy) (TEMPO)-Terminated Polystyrene
Photoreaction of C60 with Diazirine
Photoreaction of C60 with Diazobenzene Oxide
Photoreaction of C60 with Benzocyclobutenedione
Cycloaddition Reaction of C60 with 3,4-Fused Pyrrole-3-Sulfolenes
Photochemical Addition of C60 with an Amine
Photoreaction of C60 with α-Silylamines
Photoreaction of C60 with Alkyne and Alkene
Dienes
Enone and Dienone
Photoreaction of C60 with Ketene Silyl Acetals
Photoreaction of C60 with Epoxide and Cyclopropenylidene
Photoreaction of C60 with NADH and NAD Dimer Analogues
Photoreaction of C60 with Allyltributyltin
Photoreaction of C60 with Organosilicon Compounds
Photoreaction of C60 with Disulfide
Photoreaction of C60 with Sulfilimine
Cross-References
References
12 Electrochemistry and Organic Electrochemistry of Fullerenes
Introduction
Electrochemistry of Fullerenes and Their Derivatives
Fullerenes
Electrochemical Reductions
Electrochemical Oxidations
Derivatives of Fullerenes
Nature of the Addends
Number of Addends
Addition Pattern: Isomer Effect
C60 Derivatives
C70 Derivatives
Stability Difference Between Anions of Isomeric Fullerene Derivatives
Unsaturated Anionic Intermediates
Electrosynthesis of Fullerene Derivatives
C60 and C60 Derivatives
Reactions of C602-
Reactions of the Dianions of Fullerene Derivatives
1,4-(PhCH2)2C602-
1,2-(PhCH2)HC602-
C60QM2-
Reactions of C60-
Electrochemically Formation of C60 Oxazoline Derivatives: Reactions Involving PhCN
Reactions of C603-
Reactions of C60 Oxazoline Dianion with PhCH2Br and PhCD2Br: Electrochemical and H/D-Labeling Study of Oxazolino[60]Fullerene ...
The Origin of the O Atom in C60 Oxazoline: Reactions of C602- with O2 and PhCN
Electrochemical Synthesis of C70 Derivatives
Reactions of C702- with Benzyl Bromides
C70 Oxazolines
Heterocyclic Compounds
Imidazolines
Indolines
1,4,9-R3C60- Stable Intermediate
References
13 Complexation with Transition Metals
Introduction
Mononuclear Metal Complexes of Fullerenes
η1-Fashion Metal Complexes of Fullerenes
η2-Fashion Metal Complexes of Fullerenes
η5-Fashion Metal Complexes of Fullerenes
Binuclear Metal Complexes of Fullerenes
Trinuclear Metal Complexes of Fullerenes
Tetra-, Penta-, and Hexanuclear Metal Complexes of Fullerenes
Metal Cluster-Bridged Dimerizations of Fullerenes
Organometallic Polymers of Fullerenes
Reduction of Fullerenes with Metal Clusters
Conclusion
Cross-References
References
14 Transition Metal Salt-Catalyzed Reactions of [60]Fullerene
Introduction
Palladium-Catalyzed Reactions of C60
Pd-Catalyzed Allylations and Arylations of C60
Pd-Catalyzed C-H Activation Reactions of C60
Synthesis of C60-fused Heterocycles via Pd-Catalyzed C-H Activation Reactions
Pd-Catalyzed Amide-Directed C-H Activations
Pd-Catalyzed Sulfonic Acid/Hydroxy-Directed C-H Activations
Synthesis of C60-fused Carbocycles via the Pd-Catalyzed C-H Activation Reactions
Miscellaneous Pd-Catalyzed Reactions of C60
Rhodium-Catalyzed Reactions of C60
Rh-Catalyzed Hydrogenations of C60
Rh-Catalyzed Cycloaddition Reactions of C60
Rh-Catalyzed Arylations and Alkenylations of C60
Copper-Catalyzed Reactions of C60
Cu-Catalyzed Heteroannulations of C60
Cu-Catalyzed Functionalizations of Fullerene Derivatives
Other Transition Metal-Catalyzed Reactions of C60
Nickel-Catalyzed Reactions of C60
Iron-Catalyzed Reactions of C60
Silver(I)-Catalyzed Reactions of C60
Cobalt-Catalyzed Reactions of C60
Conclusion
References
15 Theoretical Prediction of Fullerene Reactivity
Introduction
Cycloaddition Reactions
Diels-Alder Cycloaddition
1, 3-Dipolar Cycloaddition
Bingel-Hirsch Reaction
[2+2] Cycloaddition Reaction
Radical Reactions
C-Centered Radicals
O-Centered Radicals
S-Centered Radicals
Addition of Metal-Centered Radicals
Addition of Hydrogen and Halogens
Carbene Additions to Fullerenes
Dihalocarbenes
Decomposition of Diazo Compounds
Decomposition of Diazirines
Conclusions
Cross-References
References
Part IV: Endofullerenes
16 Introduction and Classification of Endohedral Metallofullerenes
Introduction
Classification
Mono-EMFs
Di-EMFs
Tri-EMFs
Cluster-EMFs
Nitride Clusterfullerenes (NCFs)
Carbide Clusterfullerenes (CCMFs)
Oxide Clusterfullerenes (OCFs)
Sulfide Clusterfullerenes (SCFs)
Hydrocarbide Clusterfullerenes (HCCFs), Carbonitride Clusterfullerenes (CNCFs), and Cyanide Clusterfullerenes (CYCFs)
Hetero EMFs (aza-EMFs)
Conclusion
References
17 Preparation of Endohedral Metallofullerenes
Introduction
Synthesis and Separation of Endohedral Metallofullerenes
Synthesis of Endohedral Metallofullerenes
Direct Current Arc-Discharge Method
Nitride Cluster Fullerenes (NCFs)
Gaseous Nitrogen Source
Solid Nitrogen Source
Metal Carbide Clusterfullerenes (CCFs)
Metal Oxide/Sulfide Clusterfullerenes (OCFs and SCFs)
Metal Cyanide Clusterfullerenes (CYCFs)
Metal Hydrocarbon Clusterfullerenes (HCCFs)
Metal Carbonitride Clusterfullerenes (CNCFs)
Actinide Endohedral Metallofullerenes
Stabilization by Chemical Functionalization
Laser Ablation (or Laser Vaporization) Method
Radio Frequency Furnace Method
Ion Bombardment and Hot-Atom Chemistry Method
Extraction of Endohedral Metallofullerenes
Separation of Endohedral Metallofullerenes
Separation by Sublimation
High-Performance Liquid Chromatography (HPLC)
Chemical and Electrochemical Separation of EMFs
Summary and Outlook
References
18 Structures and Properties of Endohedral Metallofullerenes
Introduction
Molecular Structures of EMFs
Structure Characterization
Conventional Endohedral Metallofullerenes
Endohedral Clusterfullerenes
Metal Nitride Clusterfullerenes (NCFs)
Metal Carbide Clusterfullerenes (CCFs)
Metal Oxide Clusterfullerenes (OCFs)
Metal Sulfide Clusterfullerenes (SCFs)
Metal Cyanide Clusterfullerenes (CYCFs)
Metal Hydrocarbide Clusterfullerenes (HCCFs)
Metal Carbonitride Clusterfullerenes (CNCFs)
Properties of EMFs
Electronic Properties
UV-Vis-NIR Absorption Property
Electrochemical Properties
Conventional Metallofullerenes
Clusterfullerenes
Optical Properties
Luminescence Property
Nonlinear Optic Properties
Magnetic Properties
Concluding Remarks
References
19 Chemical Reactions of Endohedral Metallofullerenes
Introduction
Bingel-Hirsch Reaction
Benzyne Addition Reaction ([2 + 2] Cycloaddition Reaction)
[2 + 3] Cycloaddition Reaction
Diels-Alder Reaction
Carbene Reaction
Radical Recombination Reaction
Metal Complexation Reactions
Electrochemical Reactions of EMFs
Conclusion
References
20 Endohedral Nitrogen Fullerenes
Introduction
Discovery of Endohedral Nitrogen Fullerene
Preparation of ENF
Synthesis
Spin Enrichment
Spin Properties
Spin Hamiltonian
Spin Dynamic Properties
Clock Transitions in a Fullerene-Based Spin System
Chemical Functionalization
Chemical Reactivity of ENF
Characterization of ENF Derivatives
Amphiphilic ENF
Covalently Assembled ENF Spins
Conclusions
References
21 Lithium Endohedral Fullerenes
Introduction
Synthesis and Characterization of Li@C60
Synthesis of Li@C60
Purification of Li@C60
Characterization of li@C60
Chemical Reactivity and Modifications of Li+@C60
Counter Anion Exchange for Li+@C60
Chemical Modification for Li+@C60
Kinetic Study of Li+@C60-Involved Reaction
Kinetic Study on Diels-Alder Reaction
Neutral Li@C60, Li+@C60-
Neutralization of Li+C60 Through Electrochemistry
Device Application of Li+@C60
Endohedral Fullerenes in Photovoltaics
Li+@C60 as P-Dopant in Perovskite Solar Cells
Li+@C60 as ETL in Perovskite Solar Cells
Conclusion and Prospects
References
Part V: Nanostructures of Fullerenes and Metallofullerenes
22 Self-Assembled Aggregates of Fullerenes
Introduction
Self-Assembled Aggregates of Fullerenes
One-Dimensional Aggregates of Fullerenes
Two-Dimensional Aggregates of Fullerenes
Three-Dimensional Aggregates of Fullerenes
Self-Assembled Aggregates of Fullerene-Donor Complexes
One-Dimensional Aggregates of Fullerene-Donor Complexes
Two-Dimensional Aggregates of Fullerene-Donor Complexes
Three-Dimensional Aggregates of Fullerene-Donor Complexes
Physical Properties of Self-Assembled Aggregates of Fullerenes and Their Donor Complexes
Mechanical Properties of Self-Assembled Aggregates of Fullerenes
Optical Properties of Self-Assembled Aggregates of Fullerenes and Their Donor Complexes
Electrical Properties of Self-Assembled Aggregates of Fullerenes and Their Donor Complexes
Conclusions
References
23 Supramolecular Chemistry of Fullerenes
Introduction
Host-Guest Chemistry of Fullerenes
Supramolecular Organization of Fullerenes
Supramolecular Polymerization of Fullerene
Hybrid Materials of Supramolecular Polymers and Conventional Polymers Formed Via C60-Calix[5]arene Complexation
Conclusion
Cross-References
References
Part VI: Applications of Fullerenes and Derivatives
24 Fullerenes in Photovoltaics
Introduction
Fullerenes in Photovoltaics
Fundamentals of Photovoltaics
Fullerenes in Organic Solar Cells
Introduction to Organic Solar Cells
60-π System Acceptors
58-π System Acceptors
56-π System Acceptors
Other π System Acceptors
Fullerenes in Perovskite Solar Cells
Introduction to Perovskite Solar Cells
Fullerene Electron Transport Layers
Fullerenes as Overcoat Layers
Fullerenes as Dopants
Challenges and Prospects
References
25 Fullerene Derivatives as Antiviral and Anticancer Agents
Introduction
Anti-HIV Activities
Inhibition of HIV Protease
Inhibition of HIV Reverse Transcriptase
Anti-HCV Activities
Inhibition of HCV RNA Polymerase
Inhibition of HCV Protease
Antiproliferative Activities
Conclusion
References
26 Potential of Fullerenes for Photodynamic Therapy Application
Introduction
General Concept of Photodynamic Therapy (PDT) and Advantage in Use of Fullerenes
Photodynamic Therapy
Photoexcitation of Photosensitizers (PSs) and Generation of Reactive Oxygen Species (ROSs)
Basic Photophysical Property of Fullerenes
Water-Soluble Fullerenes
Solubility of C60
Water-Soluble Derivatives of C60 in Early Studies
Bingel-Hirsch Reaction in the Preparation of Bioactive Derivatives
Water-Soluble Derivatives by the Prato Reaction
Water-Soluble Complexes
ROS Generation from Fullerenes
1O2 Generation from C60 in Organic Solvents and Water
O2- and OH Generation in Aqueous Solution of Pristine C60/PVP Complex
Comparison of ROS Generation from Water-Soluble C60 Complexes and Derivatives in Aqueous Solution
Use of Fullerenes in Photodynamic Therapy (PDT)
Photoinduced Biological Activities of Fullerenes In Vitro
In Vivo PDT Early Studies and Recent Progress
Photodynamic Inactivation (PDI) Studies
Summary and Perspectives
References
27 Soft Materials
Introduction
Main Text
Polymeric Materials with the Distribution of Molecular Weight
Covalent Polymers
Main Chain Polymers
Pendant Polymers
End-Attached Polymers
Blends with the Polymers
Binary Blends
Ternary Blends
Materials with Unique Molecular Weight Components
Covalent Derivatives
Long-Alkylated Derivatives
Dyads
Dendrimers
Conical-Shaped Derivatives
Bent-Shaped Derivatives
Non-covalent Blends
Blends with Dendrimers
Blends with Low Molecular Weight Organic Gelators
References
28 Superconductivity
Introduction
History of Finding Superconductivity in C60
Updated Phases of Alkali, Alkaline-Earth, and Rare-Earth Metal Intercalated C60 Fullerides
The Mechanism of Superconductivity
Epilogue
Cross-References
References
Part VII: Formation Mechanism of Fullerenes/Metallofullerenes
29 Formation Mechanism of Fullerenes/Metallofullerenes
Introduction
The ``Bottom-Up´´ and ``Top-Down´´ Formations
The Bottom-Up Theory
Pentagon Road
Fullerene Road
The Top-Down Theory and Shrinking of Giant Fullerenes
Structural Relation of Metallofullerene Cages
Concluding Remarks
Cross-References
References
Index
