Preface ...................................................... xiii
List of Contributors ........................................... xv
Contents of Volumes 1 and 2 ................................... xxi
1 Chemistry with Fullerene Building Blocks ..................... 1
Julien Iehl, Maxence Urbani and Jean-Fran çois Nierengarten
1 Introduction ................................................. 1
2 Fullerene Building Blocks for Porphyrin Synthesis ............ 2
3 Fullerene Building Blocks for Dendrimer Synthesis ............ 6
3.1 Divergent synthesis ..................................... 8
3.2 Convergent synthesis ................................... 10
4 Click Chemistry with Fullerene Building Blocks .............. 16
4.1 Click chemistry with fullerene mono- and bis-adducts ... 16
4.2 Click chemistry with fullerene hexa-adducts ............ 22
5 Conclusions and Perspectives ................................ 28
References ..................................................... 28
2 New Reactivity in Fullerene Chemistry ....................... 33
Marta Izquierdo, Salvatore Filippone, Ángel Martín-
Domenech and Nazario Martín
1 Introduction ................................................ 33
2 Regioselective Intramolecular cis-1 Cycloadditions to
Fullerenes .................................................. 34
2.1 Intramolecular nucleophilic addition of phenols ........ 35
2.2 Intramolecular nucleophilic addition of alcohols and
thiols ................................................. 37
3 Fuller-1,6-enynes: New and Versatile Building Blocks in
Fullerene Chemistry ......................................... 38
3.1 The Pauson-Khand reaction on [60]fullerene ............. 39
3.2 Thermally induced [2+2] cyclizations from fuller-
1,6-enynes ............................................. 45
3.3 Thermally induced intramolecular ene reaction of
fuller-1,6-enynes: synthesis of fulleroallenes ......... 46
3.4 Theoretical study of the thermal intramolecular
reactions of fuller-1,6-enynes ......................... 47
4 Catalytic Enantioselective Cycloadditions: Chiral
Fullerenes .................................................. 49
References 55
3 Phthalocyanine Functionalized Carbon Nanostructures ......... 59
Uwe Hahn, David González-Rodríguez and Tomás Torres
1 Introduction ................................................ 59
2 Phthalocyanine-Fullerene Assemblies ......................... 60
2.1 Covalent phthalocyanine-fullerene systems .............. 61
2.2 Non-covalent phthalocyanine-fullerene systems .......... 75
3 Phthalocyanine-CNT Assemblies ............................... 83
3.1 Covalent phthalocyanine-carbon nanotube systems ........ 84
3.2 Non-covalent phthalocyanine-carbon nanotube systems .... 89
4 Conclusions and Perspectives ................................ 93
Acknowledgments ................................................ 94
References ..................................................... 94
4 Perfluoroalkylation of Fullerenes .......................... 101
Olga V. Boltalina, Igor V. Kuvychko, Natalia B. Shustova
and Steven H. Strauss
1 Methods of Synthesis ....................................... 102
1.1 General remarks ....................................... 102
1.2 In situ formation of PFAFs in an arc generator or
mass spectrometer ..................................... 103
1.3 Synthesis of PFAFs: reactions with metal
trifluoroacetates ..................................... 105
1.4 Synthesis of PFAFs: reactions with perfluoroalkyl
iodides ............................................... 107
1.4.1 Reactions with CF3I ............................ 108
1.4.2 Reactions with RFJ (RF = C2F5, C3F7, C4F9,
C6F13, and C12F25) .............................. 112
2 Methods of Isolation and Characterization .................. 115
2.1 Selective syntheses of PFAFs .......................... 115
2.2 Purification methods .................................. 119
2.3 Characterization ...................................... 123
2.3.1 Mass spectrometry .............................. 123
2.3.2 Vibrational and UV-vis spectroscopy ............ 125
2.3.3 NMR spectroscopy ............................... 127
2.3.4 X-ray crystallography .......................... 128
3 Physical Properties ........................................ 134
4 Electrochemical Properties ................................. 135
5 Chemical Properties ........................................ 137
6 Conclusions and Perspectives ............................... 139
References .................................................... 139
5 New Vistas in Endohedral Metallofullerenes ................. 145
Michio Yamada, Takeshi Akasaka and Shigeru Nagase
1 Introduction 146
2 Cage Frameworks, Positions, and Movements of Encaged
Species .................................................... 147
2.1 Monometallofullerenes ................................. 147
2.2 Dimetallofullerenes ................................... 149
2.3 Clusterfullerenes ..................................... 153
3 Electronic Properties of Pristine Endohedral
Metallofullerenes .......................................... 154
4 Chemistry of Endohedral Metallofullerenes .................. 156
4.1 Bis-silylation ........................................ 156
4.2 Electrophilic carbene addition ........................ 160
4.3 1,3-Dipolar cycloaddition ............................. 165
4.4 Nucleophilic addition ................................. 168
4.5 Diels-Alder reaction .................................. 170
4.6 Radical reaction ...................................... 173
5 Electronic Tuning by Chemical Functionalization ............ 175
6 Conclusions and Perspectives ............................... 180
Acknowledgments ............................................... 180
References .................................................... 180
6 Metallic Oxide Clusters in Fullerene Cages ................. 185
Steven Stevenson
1 Introduction ............................................... 186
2 Synthesis .................................................. 188
2.1 Historical perspective on oxometallic fullerene
(OMF) and metallic nitride fullerene (MNF)
synthesis ............................................. 188
2.2 Electric-arc synthesis of OMFs ........................ 189
3 Isolation .................................................. 191
3.1 Stir and Filter Approach (SAFA) for Sc4O2@C80 and
Sc4O3@C80 ............................................. 192
3.2 Selective precipitation method using Lewis acids ...... 196
3.2.1. Isolation of a Stage 1 metallofullerene
(eS, Sc4O3@C80) ................................ 198
3.2.2. Isolation of a Stage 2 metallofullerene
(e.g., Sc2O@C82) ............................... 199
4 Reactivity ................................................. 200
4.1 Reactivity comparison with other fullerenes ........... 200
4.2 Reactivity comparison to electrochemical band gap ..... 201
5 UV Characterization ........................................ 203
6 Conclusions and Perspectives ............................... 203
Acknowledgments ............................................... 203
References .................................................... 203
7 Synthesis of Electron Donor-[60]Fullerene Multi-Ring
Interlocked Systems ........................................ 207
Jackson D. Megiatto, Jr. and David I. Schuster
1 Introduction ............................................... 207
2 Electron Transfer Reactions in Artificial Photosynthetic
Systems .................................................... 209
3 Supramolecular Artificial Photosynthesis - Catenanes and
Rotaxanes .................................................. 210
4 Synthesis of Ferrocene-C60-Rotaxane ........................ 216
5 Synthesis of Zn(II)-Porphyrin-"Stoppered"-C60-Rotaxane ..... 221
6 Synthesis of Zn(II)-Porphyrin-C60-[2]Catenates ............. 224
7 Structural Characterization ................................ 226
8 Synthesis of [3]Gatenates .................................. 228
9 Conclusion and Perspectives ................................ 238
References .................................................... 240
8 Solubilized Carbon Nanotubes and Their Redox Chemistry ..... 245
Naotoshi Nakashima, Yasuhiko Tanaka and Tsuyohiko
Fujigaya
1 Introduction ............................................... 245
2 Characterizations of Individually Solubilized Carbon
Nanotubes .................................................. 247
3 Individual Solubilization of SWNTs Using Surfactant
Micelles ................................................... 247
4 DNA/Carbon Nanotube Hybrids ................................ 249
5 Individual Solubilization of SWNTs Using Functional
Aromatic Molecules ......................................... 251
6 Nanotube/Polymer Composites ................................ 254
7 Redox Reaction and Determination of Electronic States of
Carbon Nanotubes ........................................... 254
8 Electrocatalyst for Fuel Cell using Soluble CNTs ........... 258
9 Concluding Remarks ......................................... 262
References .................................................... 263
9 Recent Advances in Covalent Functionalization and
Characterization of Carbon Nanotubes ....................... 271
Maria Antonia Herrero, Ester Vazquez and Maurizio Prato
1 Introduction ............................................... 272
2 Carbon Nanotubes: Type, Structure and Properties ........... 273
3 Synthesis of Carbon Nanotubes .............................. 274
4 Characterization of CNTs ................................... 276
4.1 Thermogravimetric analysis ............................ 276
4.2 Spectroscopic characterization ........................ 278
4.2.1 Electron energy loss spectroscopy (EELS) ....... 278
4.2.2 Resonance Raman spectroscopy ................... 278
4.2.3 UV-vis-NIR absorption spectroscopy ............. 280
4.2.4 Infrared spectroscopy .......................... 282
4.2.5 Emission spectroscopy .......................... 283
4.2.6 Nuclear magnetic resonance spectrometry ........ 284
4.2.7 X-ray photoelectron spectroscopy ............... 285
4.3 Scanning probe microscopy ............................. 285
4.3.1 Atomic force microscopy ........................ 286
4.3.2 Scanning tunneling microscopy .................. 287
4.4 Electron microscopy ................................... 289
4.4.1 Transmission electron microscopy ............... 289
4.4.2 Scanning electron microscopy ................... 289
5 Organic Functionalization of CNTs .......................... 291
5.1. Covalent surface chemistry of CNTs ................... 291
5.1.1 Amidation and esterification of oxidized
CNTs ........................................... 292
5.1.1.1 Esterification reactions .............. 292
5.1.1.2 Amidation reactions ................... 293
5.1.2 Covalent sidewall (and tip)
functionalization .............................. 295
5.1.2.1 Halogenation .......................... 296
5.1.2.2 Addition of carbenes and nitrenes ..... 297
5.1.2.3 1,3-dipolar cycloaddition ............. 298
5.1.2.4 Diels-Alder cycloadditions ............ 301
5.1.2.5 Nucleophilic and electrophilic
additions ............................. 303
5.1.2.6 Free-radical additions ................ 304
5.1.2.7 Reduction and reductive alkylations ... 305
5.1.2.8 Direct arylations ..................... 306
5.1.2.8.1 Diazonium coupling ......... 306
5.1.2.8.2 C-C coupling chemistry
catalyzed by palladium ..... 308
5.1.2.9 Ozonolysis ............................ 308
5.1.2.10 Grafting of polymers .................. 309
5.1.2.11 Mechanochemical functionalizations .... 310
5.2 Non-covalent adsorption or wrapping of functional
molecules ............................................. 310
5.3 The endohedral filling of the CNTs inner empty
cavity ................................................ 311
6 Double functionalization reactions ......................... 312
7 Applications: Supramolecular Chemistry ..................... 312
Conclusions and Perspectives .................................. 315
References .................................................... 316
10 Reactions and Retro-Reactions of Fullerenes ................ 325
Angy L. Ortiz, Luis Echegoyen, Juan Luis Delgado and
Nazario Martín
1 Introduction ............................................... 326
2 Retro-Diels Alder Reaction ................................. 327
2.1 Thermal vs. electrochemical stability of Diels-Alder
adducts ............................................... 327
2.2 Tether-directed remote functionalization .............. 333
2.3 Orthogonal transposition approach ..................... 335
2.4 Diels-Alder adducts of substituted isobenzofurans
and C60 ............................................... 337
3 Retro-cyclopropanation Reaction ............................ 339
3.1 Electrochemically induced retro-cyclopropanation
reactions ............................................. 340
3.1.1 C60 Fullerene derivatives ...................... 340
3.1.1.1 Walk-on-the-sphere rearrangements ..... 350
3.1.2 C70 Fullerene derivatives and higher
fullerenes ..................................... 352
3.2 Chemical retro-cyclopropanation reaction .............. 355
3.2.1 Tandem reductive ring opening-retro-Bingel
reaction ....................................... 357
4 Retro-1,3-dipolar Cycloaddition Reactions .................. 357
4.1 Chemical retro-cycloaddition of pyrrolo[3,4:1,2]
[60]fullerenes ........................................ 359
4.1.1 Electrochemical retro-cycloaddition
of pyrrolo[3,4:1,2] [60]fullerenes ............. 362
4.1.2 Endohedral derivatives and their stability ..... 363
4.2 Retro-cycloaddition reaction of isoxazolo[3,4:1,2]
[60]fullerenes ........................................ 364
4.2.1 Chemical retro-cycloaddition ................... 365
4.2.2 Electrochemical retro-cycloaddition ............ 365
4.3 Retro-cycloaddition reaction of pyrazolino[3,4:1,2]
[60]fullerenes ........................................ 366
4.3.1 Chemical retro-cycloaddition ................... 366
4.3.2 Competitive retro-cycloaddition of fullerene
dimers ......................................... 367
5 Conclusions and Outlook .................................... 368
Acknowledgments ............................................... 369
References .................................................... 369
11 Porphyrin-Fullerene Supramolecular Chemistry ............... 375
Peter D. W. Boyd, Ali Hosseini, John D. van Paauwe and
Christopher A. Reed
1 Introduction ............................................... 375
2 Molecular Porphyrin Hosts for Fullerenes ................... 376
3 The Porphyrin-Fullerene Interaction ........................ 378
4 Cobalt(II) Porphyrins and Fullerenes ....................... 380
4.1 Synthesis of bis-porphyrins ........................... 381
4.2 Binding constants and charge transfer bands ........... 381
4.3 X-ray structures of T3,4,5-OMcPP cocrystallates ........ 383
5 Conclusions ................................................ 387
Acknowledgments ............................................... 387
References .................................................... 387
12 Supramolecular Hosts for Pristine Fullerenes ............... 391
Paris E. Georghiou
1 Introduction ............................................... 391
2 Complexation in Organic Solutions .......................... 392
2.1 General considerations ................................ 392
2.2 Calixarene-type hosts ................................. 393
2.3 Porphyrin-containing hosts ............................ 395
2.4 Tetrathiafulvalene-containing hosts ................... 397
2.5 Some other hosts ...................................... 399
3 Conclusions ................................................ 402
References .................................................... 402
Cumulative Index of Volumes 1 and 2
|
