Fulleranes (eBook)

Foreword 6
Preface 9
Contents 12
Chapter 1 14
Fulleranes and Carbon Nanostructures in the Interstellar Medium 14
1.1 Introduction 15
1.2 General Properties of Fullerenes 16
1.2.1 Icosahedric Fullerenes 16
1.2.1.1 Photoabsorption Spectra 16
1.2.2 Fullerenes with Multiple Spheric Layers: Buckyonions 18
1.2.3 Fulleranes: Hydrogenated Fullerenes 20
1.3 Formation of Fullerenes and Fulleranes in Astrophysical Environments 20
1.3.1 Meteorites 20
1.3.2 Carbon Stars and Planetary Nebulae 21
1.3.3 Formation of Fullerenes and Buckyonions 22
1.4 Fullerenes in the Interstellar Medium 23
1.4.1 Interstellar Extintion and the UV Bump 23
1.4.2 Theoretical Spectra and the 2,175 Å Band 24
1.4.3 Carbon Fraction in Fullerenes and Buckyonions 25
1.4.4 Diffuse Interstellar Bands 26
1.4.5 The Hydrogenation of Fullerenes in the Interstellar Medium 30
1.5 Anomalous Microwave Emission and Hydrogenated Fullerenes 31
1.5.1 Electric Dipole and Inertia Moment of Fulleranes 31
1.5.2 Rotation and Electric Dipole Emisivity from Fulleranes 32
1.5.3 Electric Dipole Emissivity from Fulleranes 34
1.6 Conclusions 36
References 36
Chapter 2 39
Infrared and Ultraviolet Spectra of Fulleranes: HREELS Studies and Implications for the Interstellar Medium 39
2.1 Introduction 39
2.2 The Unidentified Infrared Emission Problem 40
2.3 The Ultraviolet Extinction Curve 41
2.4 Experimental Procedures 41
2.5 Results 42
2.5.1 Infrared Spectra 42
2.5.2 Ultraviolet Spectra 44
2.6 Conclusions 48
References 48
Chapter 3 50
The Potential Role Played by the Fullerene-Like Structures of Interstellar Carbon Dust in the Formation of Molecular Hydrogen 50
3.1 General Aspects About Molecular Hydrogen Formation in the Interstellar Medium 50
3.2 Surfaces Involved in the Synthesis of Molecular Hydrogen in the Interstellar Medium 52
3.3 Carbon Surfaces and Molecular Hydrogen Formation 54
3.4 Fullerene-Like Structures on Carbon Dust of the Interstellar Medium: Their Role in Molecular Hydrogen Formation 55
3.5 On the Reversibility of Hydrogen Chemisorption and Release from Fulleranes 60
3.6 Thermal Decomposition of C70H38 and Formation of C70 61
3.7 Conclusions 63
References 63
Chapter 4 65
Thermodynamic Properties of Fullerene Hydrides C60H2n and Equilibria of Their Reactions 65
4.1 Introduction 65
4.2 Isomerism of C60H2n Fullerene Hydrides 67
4.2.1 Isomeric Composition of C60H2 67
4.2.2 Isomeric Composition of C60.H4 67
4.2.3 Isomeric Composition of C60.H6 68
4.2.4 Isomeric Composition of C60.H18 69
4.2.5 Isomeric Composition of C60.H36 70
4.2.6 Isomeric Composition of C60.H60 71
4.3 Experimental Investigation of Thermodynamic Properties for C60H2n 72
4.4 Thermodynamic Properties of C60H2n in the Ideal-Gas State 73
4.4.1 Quantum-Chemical Calculations of Molecular Parameters for C60.H2n 74
4.4.2 Thermodynamic Properties of C60H2n in the Ideal-Gas State 77
4.4.3 Calculation of .f..Hom for C60H2n in the Ideal-Gas State 77
4.4.4 Thermodynamics of Hydrogenation Reactions for Hydrocarbons and Fullerene C60 in the Gas State 80
4.5 Thermodynamic Properties of C60H2n Crystals 81
4.5.1 Heat Capacity and Derived Thermodynamic Properties of C60.H2n Crystals 81
4.5.2 Formation and Sublimation Enthalpies for C60H2n Crystals 84
4.6 Equilibria of Reactions of C60H2n Hydrides 85
4.6.1 Gas-Phase Hydrogenation C60 + nH2 = C60H2n 85
4.6.2 Hydrogenation C60(cr)+ nH2(g) = C60H2n(cr) 86
4.6.3 Hydrogenation with DHA 89
4.6.4 Is It Possible to Synthesize C60.H60? 90
4.7 Conclusion 91
References 92
Chapter 5 94
Fulleranes by Direct Reaction with Hydrogen Gas at Elevated Conditions 94
5.1 Introduction 94
5.2 Hydrogenation of Fullerenes by Hydrogen Gas: Conditions and Characterization of Products 96
5.3 Mass Spectrometric Characterization of Complex Fullerane Mixtures 102
5.4 High Pressure (GPa) Methods of Fullerane Synthesis 105
5.5 Future Outlook 108
5.5.1 Fulleranes with Composition C60Hx and Number of Hydrogen atoms X Below 60 108
5.5.2 Fragmented Fullerenes, e.g. C59Hx, C58Hx etc. 109
5.5.3 Fullerene Fragments 109
5.5.4 Hydrogenation of Peapods 109
References 110
Chapter 6 113
Chemical Methods to Prepare [60]Fulleranes 113
6.1 Introduction 114
6.2 C60H2 114
6.3 [60]Fulleranes with More Than 2 But Less Than 18 Hydrogens: C60H2< n<
6.4 C60H18 120
6.5 C60H36 124
6.6 [60]Fulleranes With More Than 36 Hydrogens: C60H> 36
6.7 Conclusion 130
6.8 Author Biographies 131
References 131
Chapter 7 134
Synthesis, Stability and Spectroscopy of Perdeuterofulleranes: C60D36 and C70D38 134
7.1 Introduction 134
7.2 Experimental 135
7.2.1 Materials and Equipment 135
7.2.2 Synthesis of C60H38 in n-Hexane 136
7.2.3 Synthesis of C70H38 in n-Hexane 136
7.2.4 Synthesis of Perdeuterofullerane 136
7.2.5 Synthesis of C70H38 in Toluene 137
7.2.6 Synthesis of C70H38 in Benzene 137
7.2.7 Synthesis of C70.D38 in Toluene 137
7.3 Results and Discussion 138
7.3.1 Electronic Absorption Spectra of C60.H36 and C60.D36 138
7.3.2 The Electronic Absorption Spectra of Fulleranes C70.H38 and C70D38 139
7.3.3 Aspects on Deuteration: the Isotope Effect 141
7.3.4 FT-IR Spectroscopy of C60.D36 and C60.H36 142
7.3.5 FT-IR Spectroscopy of C70.D38 and C70.H38 144
7.3.6 Thermal Analysis (TGA, DTG and DTA) of C60.D36 and C60.H36 146
7.3.7 Thermal Stability of C70D38 in Comparison to C70H38 148
7.3.8 Stability of C60D36 Exposed to Air at Room Temperature 150
7.3.9 Oxidation Stability of C70D38 and C70H38 152
References 154
Chapter 8 156
Isotope Effect in the UV Photolysis of Hydrogenated and Perdeuterated Fulleranes 156
8.1 Introduction 157
8.2 Experimental 158
8.2.1 Reagents and Equipment 158
8.2.2 Photolysis of C60H36 159
8.2.3 Photolysis of C60D36 160
8.2.4 Photolysis of C70H38 160
8.2.5 Photolysis of C70D38 160
8.2.6 Preparation of C60H18 in n-Hexane and Subsequent Photolysis Under He 161
8.2.7 Preparation of C60D18 in n-Hexane and Subsequent Photolysis Under He 161
8.2.8 Photolysis of C3n Isomer of C60H18 in Tetradecane Under Ar 162
8.3 Results and Discussion 162
8.3.1 Kinetics of the Fulleranes C60H36 and C60D36 Photolysis 162
8.3.2 Photolysis of C70H38 and C70D38 165
8.3.3 Photolysis of C60H18 and C60D18 in n-Hexane Under Helium: Determination of the Kinetic Isotope Effect 167
8.3.4 Photolysis of C3n-C60H18 in Tetradecane Under Ar 170
8.3.5 Discussion of the Photolysis Data in an Astrochemical Context 172
8.3.6 Photolysis Stability of C60H36: A Comparison with Other Fulleranes and with Polyynes 175
8.4 Conclusions 175
References 176
Chapter 9 178
Characterization of Hydrogenated Fullerenes by NMR Spectroscopy 178
9.1 Introduction 178
9.2 Synthesis and Sample Preparation 180
9.3 1H NMR Spectroscopy 181
9.4 13C NMR Spectroscopy 184
9.5 Two-Dimensional NMR Techniques 188
9.6 3He-NMR Spectroscopy 190
9.7 Specific Isomers of Hydrogenated Fullerenes Studied with NMR Spectroscopy 194
9.7.1 C60H2 194
9.7.2 C60H4 196
9.7.3 C60H6 198
9.7.4 C60H18 199
9.7.5 C60H36 200
9.7.6 C70H2 202
9.7.7 C70H4 203
9.7.8 C70H8 204
9.7.9 C70H10 205
9.7.10 C70H38 205
9.8 Conclusions 206
References 207
Chapter 10 210
Low Temperature Infrared Spectroscopy of C60 and C70 Fullerenes and Fullerane C60H18 210
10.1 Introduction 211
10.2 Experimental 211
10.2.1 Materials and Equipment 211
10.2.2 Experimental Procedure 212
10.3 Results and Discussion 213
10.3.1 The Low Temperature and High Temperature Gas Phase FT-IR Spectra of C60 Fullerene 213
10.3.2 The Low Temperature and High Temperature Gas Phase FT-IR Spectra of C70 Fullerene 219
10.3.3 The Low Temperature FT-IR Spectra of C60.H18 Fullerane 223
10.3.4 The Low Temperature FT-IR Spectra of Mixture of Fulleranes C60Hx (77%) and C70Hy (22%) 227
10.4 Conclusions 229
References 230
Chapter 11 231
High-Pressure Hydrogenated Carbon Nanostructures 231
11.1 Experimental Methods for Testing of Samples 233
11.2 High-Pressure Hydrogenated Single-Walled Carbon Nanotubes and Nanofibers 234
11.3 High-Pressure Hydrogenated C60 247
References 255
Chapter 12 257
Topological Modeling of C60H36 Hydrides 257
12.1 Introduction 257
12.2 Topological Model 262
12.3 Topological Modeling of C60H18 264
12.4 Topological Modeling of C60H36 268
12.5 C60H36 Isomers with Extremal W or r Values 274
12.5.1 C60H36(C1*) 274
12.5.2 C60H36(C1*)(2) 274
12.6 C60H36(C3*) 276
12.7 Conclusions 277
References 277