FULLERENES. Nanochernistry, Nanomagnetisniy. Nanophotonics. Nanomedicine, Elena Sheka. CRC Press. Taylor fx Francis Group
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1 FULLERENES Nanochernistry, Nanomagnetisniy Nanomedicine, Nanophotonics Elena Sheka CRC Press Taylor fx Francis Group Boca Raton London NewYork CRC Press is an imprint of the Taylor & Francis Group, an Informs business
2 Contents Preface About the author Acknowledgments xi xiii xv Chapter 1 Concepts and grounds Why odd electrons and not ji electrons? Donor-acceptor ability as a leitmotiv of intermolecular interaction of fullerenes Energy terms of ground and excited states of a binary complex with intense D-A interaction Ionic components of a D-A binary system Odd electrons approach as a basic concept of nanoscience 13 References 14 Chapter 2 Grounds of computational science of fullerenes Unrestricted broken symmetry approach: Basic relations UBS approach realization in semiempirical calculation UBS HF approach testing UBS HF approach and fullerene nanoscience 28 References 29 Chapter 3 Fullerene C60 in view of the unrestricted broken symmetry Hartree-Fock approach Introduction Structure and symmetry C60 shape symmetry: Structural experiments C60 shape symmetry: Quantum chemical calculations C60 shape symmetry: Optical spectra Continuous symmetry concept Continuous symmetry of fullerene C60 and its monoderivatives Continuous symmetry view on optical electronic spectra of fullerene C60 and its derivatives 45 v
3 vi Contents 3.3 Total spin (S2) Chemical reactivity of fullerenes C60 and C Chemical portrait of fullerene C Chemical portrait of fullerene C C60 isomers Concluding remarks 60 References 61 Chapter 4 Nanochemistry of fullerene C60: Stepwise computational synthesis of fluorinated fullerenes C60F2jt Introduction Background and the problem formulation A historical background ACS algorithm of computational synthesis of fullerenes' derivatives Reactions of C60 fluorination Start of C60 fluorination C60F2-C60F8 adducts C60F10-C60F18 adducts C60F20-C60F36 adducts C60F38-C60F48 adducts C60F50-C60F60 adducts Fluorination-induced C60 cage structure transformation Concluding remarks 91 References 91 Chapter 5 Nanochemistry of fullerene C60: Hydrogenated fullerenes from C60 to C60H Grounds of computational methodology C6D hydrogenation as algorithmic process Comparative efficacy of fluorination and hydrogenation reactions C60 cage structure transformation during hydrogenation Comparison with experiments Concluding remarks Ill References Ill Chapter 6 Nanochemistry of fullerene C60: Cyano- and azo-polyderivatives Introduction Grounds of computational methodology Polyhydrocyanides QoHCCN^ and polycyanides C60(CN) Polyazoderivatives C60(NH), 120
4 Contents vii 6.5 Concluding remarks: A little about C60 chlorination 126 References 130 Chapter 7 Nanochemistry of fullerene C60: Donor-acceptor reactions of fullerene C60 with amines Introduction About intermolecular interaction and donor-acceptor chemical reactions Donor-acceptor reactions for fullerene dyads with different types of intermolecular interaction terms Methodology of a D-A dyad consideration Molecular partners Dimethylenemethylamine (DMMA) Tetrakis(dimethylamino)ethylene (TDAE) Tetrakisaminoethylene (TAE) Cyclooctylamine-5-nitropyridine (COANP) Molecular ions q0-based dyads Dyad C60-DMMA Dyad C60-TDAE Dyad C60-TAE Dyad C60-COANP Concluding remarks about donor-acceptor chemical reactions of fullerene C References 147 Chapter 8 Nanochemistry of fullerene C60: C60 dimerization and oligomerization Introduction Ground-state term of the C60-C60 dyad Dimerization mechanisms Photoexcitation technology Thermal and high-pressure technologies Plasma and electron beam processing Field-stimulated formation and decomposition of dimers C50 oligomers Polymerization grounds Structural data Binding energies in oligomers Concluding remarks about the character of chemical reactions typical to fullerene 169 References ^
5 viii Contents Chapter 9 Nanomedicine of fullerene C Introduction Spin-flip in the oxygen molecule in fullerene solutions Fullerene-silica complexes for medicinal chemistry C60 fullerene-highly dispersed silica composite Aerosil (PNSS) Silica gel (SCG) Aerogel Fullerosil Fullerosilica gel Concluding remarks on the nature of the biological activity of fullerene 190 References 191 Chapter 10 Nanophotonics of f ullerenes Introduction Schematic characterization of the excited states and optical spectra of fullerenes in solution Electromagnetic theory of enhanced optical effects Absorption and emission spectra of fullerenes in solution Quantum chemical analysis of intermolecular interactions in solutions of fullerenes 207 of nonlinear 10.6 Blue emission, pairwise interaction, and efficacy optical 10.7 And again about blue emission, photodynamic therapy, and behavior 211 nanophotonics 10.8 Nanophotonics of fullerenes in chemistry, medicine, and of fullerene solutions 215 optics 217 References 218 Chapter 11 Odd electron-enhanced chemical reactivity of carbon nanotubes Introduction Chemical reactivity of carbon nanotubes (4,4) Single-walled carbon nanotubes Fragments of group Fragments of group Fragments of group (n,n) and (m,0) Single-walled carbon nanotubes (n,n) Single-walled carbon nanotubes (m,0) Single-walled carbon nanotubes General view on single-walled carbon nanotubes' chemical reactivity Comparison with experiment 237
6 Contents ix 11.5 Electronic characteristics of single-walled carbon nanotubes 238 References 240 Chapter 12 Chemical reactivity of graphene, Introduction Broken symmetry Hartree-Fock approach to chemical reactivity of graphene Carbon nanotube-graphene composites Grounds for the computational synthesis of (l)k (II), composites Hammer (I)12 (II)W composites Composites Composites II Composites III Composites IV Cutting-blade (I)a>2 (II)1/2 composites Composites V Cross-sections VI Composites VII and VIII Composites IX Cross-section X Composites XI Composite XII Concluding remarks Synopsis of features concerned with chemical reactivity of nanocarbons, Fullerenes Single-walled nanotubes Graphene 262 References 262 Chapter 13 Magnetism of fullerenes and graphene Introduction Why are C60 and C70 molecules nonmagnetic? Effectively unpaired electrons in monomer molecules of oligomers Peculiarities in the odd electrons behavior Exchange integral/ Nanostructures and magnetism in polymeric C60 crystals Magnetism of zigzag edge nanographenes About size-dependent magnetism Odd electrons as they are seen today 278 References 278
7 X Contents Chapter 14 Chemical and structural analogs of sp2 nanocarbons Siliceous nanostructures Boron nitride hexagon-packed species 288 References 289 Chapter 15 Conclusion 291 Index 295
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