Handbook of Carbon Nano Materials, Volume 1: Syntheses and Supramolecular Systems

Contents......Page 6
Preface......Page 14
List of Contributors......Page 16
Contents of Volumes 1 and 2......Page 22
1. Introduction......Page 26
2. Fullerene Building Blocks for Porphyrin Synthesis......Page 27
3. Fullerene Building Blocks for Dendrimer Synthesis......Page 31
3.1. Divergent synthesis......Page 33
3.2. Convergent synthesis......Page 35
4.1. Click chemistry with fullerene mono- and bis-adducts......Page 41
4.2. Click chemistry with fullerene hexa-adducts.......Page 47
References.......Page 53
1. Introduction......Page 58
2. Regioselective Intramolecular cis-1 Cycloadditions to Fullerenes......Page 59
2.1. Intramolecular nucleophilic addition of phenols.......Page 60
2.2. Intramolecular nucleophilic addition of alcohols and thiols......Page 62
3. Fuller-1,6-enynes: New and Versatile Building Blocks in Fullerene Chemistry......Page 63
3.1. The Pauson–Khand reaction on [60]fullerene......Page 64
3.2. Thermally induced [2+2] cyclizations from fuller-1,6-enynes......Page 70
3.3. Thermally induced intramolecular ene reaction of fuller-1,6-enynes: synthesis of fulleroallenes......Page 71
3.4. Theoretical study of the thermal intramolecular reactions of fuller-1,6-enynes......Page 72
4. Catalytic Enantioselective Cycloadditions: Chiral Fullerenes......Page 74
References......Page 80
1. Introduction......Page 84
2. Phthalocyanine-Fullerene Assemblies......Page 85
2.1. Covalent phthalocyanine-fullerene systems.......Page 86
2.2. Non-covalent phthalocyanine-fullerene systems......Page 100
3. Phthalocyanine-CNT Assemblies......Page 108
3.1. Covalent phthalocyanine-carbon nanotube systems......Page 109
3.2. Non-covalent phthalocyanine-carbon nanotube systems......Page 114
4. Conclusions and Perspectives......Page 118
References......Page 119
4 / Perfluoroalkylation of Fullerenes Olga V. Boltalina, Igor V. Kuvychko, Natalia B. Shustova and Steven H. Strauss......Page 126
1.1. General remarks......Page 127
1.2. In situ formation of PFAFs in an arc generator or mass spectrometer......Page 128
1.3. Synthesis of PFAFs: reactions with metal trifluoroacetates.......Page 130
1.4. Synthesis of PFAFs: reactions with perfluoroalkyl iodides......Page 132
1.4.1. Reactions with CF3I......Page 133
1.4.2. Reactions with RFI (RF = C2F5, C3F7, C4F9, C6F13, and C12F25)......Page 137
2.1. Selective syntheses of PFAFs......Page 140
2.2. Purification methods......Page 144
2.3.1. Mass spectrometry......Page 148
2.3.2. Vibrational and UV-vis spectroscopy......Page 150
2.3.3. NMR spectroscopy......Page 152
2.3.4. X-ray crystallography......Page 153
3. Physical Properties......Page 159
4. Electrochemical Properties......Page 160
5. Chemical Properties......Page 162
References.......Page 164
5 / New Vistas in Endohedral Metallofullerenes Michio Yamada, Takeshi Akasaka and Shigeru Nagase......Page 170
1. Introduction......Page 171
2.1. Monometallofullerenes.......Page 172
2.2. Dimetallofullerenes......Page 174
2.3. Clusterfullerenes......Page 178
3. Electronic Properties of Pristine Endohedral Metallofullerenes......Page 179
4.1. Bis-silylation......Page 181
4.2. Electrophilic carbene addition.......Page 185
4.3. 1,3-Dipolar cycloaddition.......Page 190
4.4. Nucleophilic addition.......Page 193
4.5. Diels–Alder reaction.......Page 195
4.6. Radical reaction......Page 198
5. Electronic Tuning by Chemical Functionalization.......Page 200
References.......Page 205
6 / Metallic Oxide Clusters in Fullerene Cages Steven Stevenson......Page 210
1. Introduction......Page 211
2.1. Historical perspective on oxometallic fullerene (OMF) and metallic nitride fullerene (MNF) synthesis......Page 213
2.2. Electric-arc synthesis of OMFs......Page 214
3. Isolation......Page 216
3.1. Stir and Filter Approach (SAFA) for Sc4O2@C80 and Sc4O3@C80......Page 217
3.2. Selective precipitation method using Lewis acids......Page 221
3.2.1. Isolation of a Stage 1 metallofullerene (e.g., Sc4O3@C80)......Page 223
3.2.2. Isolation of a Stage 2 metallofullerene (e.g., Sc2O@C82)......Page 224
4.1. Reactivity comparison with other fullerenes......Page 225
4.2. Reactivity comparison to electrochemical band gap......Page 226
References.......Page 228
1. Introduction......Page 232
2. Electron Transfer Reactions in Artificial Photosynthetic Systems......Page 234
3. Supramolecular Artificial Photosynthesis — Catenanes and Rotaxanes......Page 235
4. Synthesis of Ferrocene-C60-Rotaxane......Page 241
5. Synthesis of Zn(II)-Porphyrin-“Stoppered”-C60-Rotaxane.......Page 246
6. Synthesis of Zn(II)-Porphyrin-C60-[2]Catenates......Page 249
7. Structural Characterization......Page 251
8. Synthesis of [3]Catenates......Page 253
9. Conclusion and Perspectives......Page 263
References......Page 265
1. Introduction......Page 270
3. Individual Solubilization of SWNTs Using Surfactant Micelles......Page 272
4. DNA/Carbon Nanotube Hybrids......Page 274
5. Individual Solubilization of SWNTs Using Functional Aromatic Molecules......Page 276
7. Redox Reaction and Determination of Electronic States of Carbon Nanotubes......Page 279
8. Electrocatalyst for Fuel Cell using Soluble CNTs......Page 283
9. Concluding Remarks......Page 287
References.......Page 288
9 / Recent Advances in Covalent Functionalization and Characterization of Carbon Nanotubes Maria Antonia Herrero, Ester Vazquez and Maurizio Prato......Page 296
1. Introduction......Page 297
2. Carbon Nanotubes: Type, Structure and Properties......Page 298
3. Synthesis of Carbon Nanotubes......Page 299
4.1. Thermogravimetric analysis......Page 301
4.2.2. Resonance Raman spectroscopy......Page 303
4.2.3. UV-vis–NIR absorption spectroscopy......Page 305
4.2.4. Infrared spectroscopy......Page 307
4.2.5. Emission spectroscopy......Page 308
4.2.6. Nuclear magnetic resonance spectrometry......Page 309
4.3. Scanning probe microscopy......Page 310
4.3.1. Atomic force microscopy......Page 311
4.3.2. Scanning tunneling microscopy......Page 312
4.4.2. Scanning electron microscopy......Page 314
5.1. Covalent surface chemistry of CNTs......Page 316
5.1.1.1. Esterification reactions......Page 317
5.1.1.2. Amidation reactions......Page 318
5.1.2. Covalent sidewall (and tip) functionalization......Page 320
5.1.2.1. Halogenation......Page 321
5.1.2.2. Addition of carbenes and nitrenes......Page 322
5.1.2.3. 1,3-dipolar cycloaddition......Page 323
5.1.2.4. Diels–Alder cycloadditions......Page 326
5.1.2.5. Nucleophilic and electrophilic additions......Page 328
5.1.2.6. Free-radical additions......Page 329
5.1.2.7. Reduction and reductive alkylations......Page 330
5.1.2.8.1. Diazonium coupling......Page 331
5.1.2.9. Ozonolysis......Page 333
5.1.2.10. Grafting of polymers......Page 334
5.2. Non-covalent adsorption or wrapping of functional molecules......Page 335
5.3. The endohedral filling of the CNTs inner empty cavity......Page 336
7. Applications: Supramolecular Chemistry......Page 337
Conclusions and Perspectives......Page 340
References......Page 341
10 / Reactions and Retro-Reactions of Fullerenes Angy L. Ortiz, Luis Echegoyen, Juan Luis Delgado and Nazario Martín......Page 350
1. Introduction......Page 351
2.1. Thermal vs. electrochemical stability of Diels–Alder adducts......Page 352
2.2. Tether-directed remote functionalization......Page 358
2.3. Orthogonal transposition approach......Page 360
2.4. Diels–Alder adducts of substituted isobenzofurans and C60......Page 362
3. Retro-cyclopropanation Reaction......Page 364
3.1.1. C60 Fullerene derivatives......Page 365
3.1.1.1. Walk-on-the-sphere rearrangements......Page 375
3.1.2. C70 Fullerene derivatives and higher fullerenes.......Page 377
3.2. Chemical retro-cyclopropanation reaction......Page 380
4. Retro-1,3-dipolar Cycloaddition Reactions......Page 382
4.1. Chemical retro-cycloaddition of pyrrolo[3,4:1,2] [60]fullerenes......Page 384
4.1.1. Electrochemical retro-cycloaddition of pyrrolo[3,4:1,2] [60]fullerenes......Page 387
4.1.2. Endohedral derivatives and their stability......Page 388
4.2. Retro-cycloaddition reaction of isoxazolo[3,4:1,2] [60]fullerenes......Page 389
4.2.2. Electrochemical retro-cycloaddition......Page 390
4.3.1. Chemical retro-cycloaddition.......Page 391
4.3.2. Competitive retro-cycloaddition of fullerene dimers......Page 392
5. Conclusions and Outlook......Page 393
References......Page 394
1. Introduction......Page 400
2. Molecular Porphyrin Hosts for Fullerenes......Page 401
3. The Porphyrin-Fullerene Interaction......Page 403
4. Cobalt(II) Porphyrins and Fullerenes.......Page 405
4.2. Binding constants and charge transfer bands......Page 406
4.3. X-ray structures of T3,4,5-OMePP cocrystallates......Page 408
References.......Page 412
1. Introduction......Page 416
2.1. General considerations......Page 417
2.2. Calixarene-type hosts......Page 418
2.3. Porphyrin-containing hosts.......Page 420
2.4. Tetrathiafulvalene-containing hosts......Page 422
2.5. Some other hosts......Page 424
References......Page 427
Cumulative Index of Volumes 1 and 2......Page 430