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Special Issue "Fullerene Chemistry"

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A special issue of Molecules (ISSN 1420-3049).

Deadline for manuscript submissions: closed (31 March 2012)

Special Issue Editor

Guest Editor
Prof. Dr. Kun’ichi Miyazawa

Fullerene Engineering Group, Advanced Materials Processing Unit, Advanced Key Technologies Division, National Institute for Materials Science, 1-1, Namiki, Tsukuba, Ibaraki, 305-0044, Japan
Website | E-Mail
Interests: fullerene nanowhiskers; fullerene nanotubes; fullerene nanosheets

Special Issue Information

Dear Colleagues,

Fullerene molecules have the unique closed morphologies that are totally composed of carbon atoms. They can include foreign atoms inside, and also can be attached with a variety of functional groups, which offers a great degree of freedom on their shape and properties. Hence, we can expect to produce a tremendous number of fullerene assemblies that will be useful for the application of energy, environment, biology, medicine, electronics, mechanics and so forth. Among these fullerene materials, the nanofibers made of fullerene molecules such as fullerene nanowhiskers and fullerene nanotubes are especially attractive, owing to their potential applicability for semiconductors, transistors, catalysts, sensors, molecular sieves, templates for chemical synthesis, illuminants, solar cells and so forth. The fullerene nanotubes defined here are the tubular nanofibers composed of fullerene molecules. In addition, single-crystal thin sheets made of fullerene molecules, “fullerene nanosheets”, will find a wide application as well. Hence, this special issue “Fullerene Chemistry” focuses on the synthesis, characterization and application of low-dimensional fullerene nanomaterials. Physical and chemical treatments of fullerene nanomaterials can also widen the fullerene world. Not only the fullerene nanomaterials but also carbon nanotubes and graphene are included in this special issue since they have close relationships with fullerene chemistry.

The researchers in fullerenes, carbon nanotubes and graphene are strongly encouraged to submit their recent topics to this special issue. The related review papers are also welcome.

Prof. Dr. Kun’ichi Miyazawa
Guest Edito

Keywords

  • fullerene
  • fullerene nanowhisker (nanorod, nanowire)
  • fullerene nanotube
  • fullerene nanosheet
  • carbon nanotube
  • graphene
  • application of fullerenes, carbon nanotubes and graphene

Published Papers (9 papers)

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Research

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Open AccessArticle Stability Computations for Isomers of La@Cn (n = 72, 74, 76)
Molecules 2012, 17(11), 13146-13156; doi:10.3390/molecules171113146
Received: 8 October 2012 / Revised: 26 October 2012 / Accepted: 30 October 2012 / Published: 5 November 2012
Cited by 8 | PDF Full-text (1428 KB)
Abstract Density-functional theory calculations are presented for low-energy La@C72, La@C74 and La@C76 isomers with IPR (isolated pentagon rule) and non-IPR cages. The relative isomeric production yields at high temperatures are evaluated using the calculated terms, and the relationships to observations are discussed. Full article
(This article belongs to the Special Issue Fullerene Chemistry)
Open AccessArticle Platinum Clusters on Vacancy-Type Defects of Nanometer-Sized Graphene Patches
Molecules 2012, 17(7), 7941-7960; doi:10.3390/molecules17077941
Received: 8 May 2012 / Revised: 11 June 2012 / Accepted: 19 June 2012 / Published: 2 July 2012
Cited by 5 | PDF Full-text (2272 KB)
Abstract
Density functional theory calculations found that spin density distributions of platinum clusters adsorbed on nanometer-size defective graphene patches with zigzag edges deviate strongly from those in the corresponding bare clusters, due to strong Pt-C interactions. In contrast, platinum clusters on the pristine patch
[...] Read more.
Density functional theory calculations found that spin density distributions of platinum clusters adsorbed on nanometer-size defective graphene patches with zigzag edges deviate strongly from those in the corresponding bare clusters, due to strong Pt-C interactions. In contrast, platinum clusters on the pristine patch have spin density distributions similar to the bare cases. The different spin density distributions come from whether underlying carbon atoms have radical characters or not. In the pristine patch, center carbon atoms do not have spin densities, and they cannot influence radical characters of the absorbed cluster. In contrast, radical characters appear on the defective sites, and thus spin density distributions of the adsorbed clusters are modulated by the Pt-C interactions. Consequently, characters of platinum clusters adsorbed on the sp2 surface can be changed by introducing vacancy-type defects. Full article
(This article belongs to the Special Issue Fullerene Chemistry)
Open AccessArticle Synthesis and Characterization of Positively Charged Pentacationic [60]Fullerene Monoadducts for Antimicrobial Photodynamic Inactivation
Molecules 2012, 17(5), 5225-5243; doi:10.3390/molecules17055225
Received: 31 March 2012 / Revised: 22 April 2012 / Accepted: 28 April 2012 / Published: 7 May 2012
Cited by 8 | PDF Full-text (476 KB) | Supplementary Files
Abstract
We designed and synthesized two analogous pentacationic [60]fullerenyl monoadducts, C60(>ME1N6+C3) (1) and C60(>ME3N6+C3) (2), with variation of the methoxyethyleneglycol length. Each
[...] Read more.
We designed and synthesized two analogous pentacationic [60]fullerenyl monoadducts, C60(>ME1N6+C3) (1) and C60(>ME3N6+C3) (2), with variation of the methoxyethyleneglycol length. Each of these derivatives bears a well-defined number of cationic charges aimed to enhance and control their ability to target pathogenic Gram-positive and Gram-negative bacterial cells for allowing photodynamic inactivation. The synthesis was achieved by the use of a common synthon of pentacationic N,N′,N,N,N,N-hexapropyl-hexa(aminoethyl)amine arm (C3N6+) having six attached propyl groups, instead of methyl or ethyl groups, to provide a well-balanced hydrophobicity–hydrophilicity character to pentacationic precursor intermediates and better compatibility with the highly hydrophobic C60 cage moiety. We demonstrated two plausible synthetic routes for the preparation of 1 and 2 with the product characterization via various spectroscopic methods. Full article
(This article belongs to the Special Issue Fullerene Chemistry)
Open AccessArticle Superconducting Fullerene Nanowhiskers
Molecules 2012, 17(5), 4851-4859; doi:10.3390/molecules17054851
Received: 31 March 2012 / Revised: 12 April 2012 / Accepted: 18 April 2012 / Published: 26 April 2012
Cited by 14 | PDF Full-text (478 KB)
Abstract
We synthesized superconducting fullerene nanowhiskers (C60NWs) by potassium (K) intercalation. They showed large superconducting volume fractions, as high as 80%. The superconducting transition temperature at 17 K was independent of the K content (x) in the range between 1.6 and 6.0
[...] Read more.
We synthesized superconducting fullerene nanowhiskers (C60NWs) by potassium (K) intercalation. They showed large superconducting volume fractions, as high as 80%. The superconducting transition temperature at 17 K was independent of the K content (x) in the range between 1.6 and 6.0 in K-doped C60 nanowhiskers (KxC60NWs), while the superconducting volume fractions changed with x. The highest shielding fraction of a full shielding volume was observed in the material of K3.3C60NW by heating at 200 °C. On the other hand, that of a K-doped fullerene (K-C60) crystal was less than 1%. We report the superconducting behaviors of our newly synthesized KxC60NWs in comparison to those of KxC60 crystals, which show superconductivity at 19 K in K3C60. The lattice structures are also discussed, based on the x-ray diffraction (XRD) analyses. Full article
(This article belongs to the Special Issue Fullerene Chemistry)
Open AccessArticle Synthesis and Characterization of Fullerene Nanowhiskers by Liquid-Liquid Interfacial Precipitation: Influence of C60 Solubility
Molecules 2012, 17(4), 3858-3865; doi:10.3390/molecules17043858
Received: 12 March 2012 / Revised: 23 March 2012 / Accepted: 26 March 2012 / Published: 29 March 2012
Cited by 10 | PDF Full-text (575 KB) | HTML Full-text | XML Full-text
Abstract
Fullerene nanowhiskers (FNWs) composed of C60 fullerene molecules were prepared using the liquid–liquid interfacial precipitation (LLIP) method in the carbon-disulfide (CS2) and isopropyl alcohol (IPA) system. The electron microscopic images reveal the formation of non-tubular FNWs. The X-ray diffraction (XRD)
[...] Read more.
Fullerene nanowhiskers (FNWs) composed of C60 fullerene molecules were prepared using the liquid–liquid interfacial precipitation (LLIP) method in the carbon-disulfide (CS2) and isopropyl alcohol (IPA) system. The electron microscopic images reveal the formation of non-tubular FNWs. The X-ray diffraction (XRD) pattern studies indicate the presence of fcc crystalline structure and unusual triclinic structure in the FNWs. The selected area electron diffraction pattern (SAED) analysis demonstrates the existence of triclinic and electron beam assisted fcc to tetragonal crystalline phase transformation. The formation of triclinic structure might be validated due to the partial polymerization of FNWs at C60 saturated CS2-IPA interface. The high solubility of C60 in CS2 solvent system results in partial polymerization of FNWs. The polymerization of fullerene molecules in the FNWs has been further confirmed using Raman spectroscopy. Full article
(This article belongs to the Special Issue Fullerene Chemistry)
Open AccessArticle Synthesis of Endohedral Metallofullerene Glycoconjugates by Carbene Addition
Molecules 2011, 16(11), 9495-9504; doi:10.3390/molecules16119495
Received: 18 October 2011 / Revised: 3 November 2011 / Accepted: 10 November 2011 / Published: 14 November 2011
Cited by 9 | PDF Full-text (450 KB) | Supplementary Files
Abstract
Endohedral metallofullerene glycoconjugates were synthesized under mild conditions by carbene addition using appropriate glycosylidene-derived diazirine with La2@Ih-C80. NMR spectroscopic studies revealed that the glycoconjugate consists of two diastereomers of [6,6]-open mono-adducts. The electronic properties were characterized
[...] Read more.
Endohedral metallofullerene glycoconjugates were synthesized under mild conditions by carbene addition using appropriate glycosylidene-derived diazirine with La2@Ih-C80. NMR spectroscopic studies revealed that the glycoconjugate consists of two diastereomers of [6,6]-open mono-adducts. The electronic properties were characterized using Vis/NIR absorption spectroscopy and electrochemical measurements. This study demonstrates that glycosylidene carbene is useful to incorporate carbohydrate moieties onto endohedral metallofullerene surfaces. Full article
(This article belongs to the Special Issue Fullerene Chemistry)
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Review

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Open AccessReview Coordination Modes and Different Hapticities for Fullerene Organometallic Complexes
Molecules 2012, 17(6), 7151-7168; doi:10.3390/molecules17067151
Received: 10 April 2012 / Revised: 22 May 2012 / Accepted: 1 June 2012 / Published: 12 June 2012
Cited by 12 | PDF Full-text (924 KB)
Abstract
The different coordination modes in fullerene organometallic complexes are reviewed. The main modes are η2 and η5, but there are some interesting studies about the other four, all of them are revised in order to show which is the state of art of
[...] Read more.
The different coordination modes in fullerene organometallic complexes are reviewed. The main modes are η2 and η5, but there are some interesting studies about the other four, all of them are revised in order to show which is the state of art of this kind of compounds with the respect of the hapticity. Full article
(This article belongs to the Special Issue Fullerene Chemistry)
Open AccessReview Chemistry of Fullerene Epoxides: Synthesis, Structure, and Nucleophilic Substitution-Addition Reactivity
Molecules 2012, 17(6), 6395-6414; doi:10.3390/molecules17066395
Received: 28 March 2012 / Revised: 14 May 2012 / Accepted: 16 May 2012 / Published: 25 May 2012
Cited by 14 | PDF Full-text (410 KB)
Abstract
Fullerene epoxides, C60On, having epoxide groups directly attached to the fullerene cage, constitute an interesting class of fullerene derivatives. In particular, the chemical transformations of fullerene epoxides are expected to play an important role in the development of functionalized
[...] Read more.
Fullerene epoxides, C60On, having epoxide groups directly attached to the fullerene cage, constitute an interesting class of fullerene derivatives. In particular, the chemical transformations of fullerene epoxides are expected to play an important role in the development of functionalized fullerenes. This is because such transformations can readily afford a variety of mono- or polyfunctionalized fullerene derivatives while conserving the epoxy ring arrangement on the fullerene surface, as seen in representative regioisomeric fullerene polyepoxides. The first part of this review addresses the synthesis and structural characterization of fullerene epoxides. The formation of fullerene epoxides through different oxidation reactions is then explored. Adequate characterization of the isolated fullerene epoxides was achieved by concerted use of NMR and LC-MS techniques. The second part of this review addresses the substitution of fullerene epoxides in the presence of a Lewis acid catalyst. Most major substitution products have been isolated as pure compounds and their structures established through spectroscopic methods. The correlation between the structure of the substitution product and the oxygenation pattern of the starting materials allows elucidation of the mechanistic features of this transformation. This approach promises to lead to rigorous regioselective production of various fullerene derivatives for a wide range of applications. Full article
(This article belongs to the Special Issue Fullerene Chemistry)
Open AccessReview Recent Advances in Photoinduced Electron Transfer Processes of Fullerene-Based Molecular Assemblies and Nanocomposites
Molecules 2012, 17(5), 5816-5835; doi:10.3390/molecules17055816
Received: 29 March 2012 / Revised: 3 May 2012 / Accepted: 8 May 2012 / Published: 16 May 2012
Cited by 75 | PDF Full-text (919 KB)
Abstract
Photosensitized electron-transfer processes of fullerenes hybridized with electron donating or other electron accepting molecules have been surveyed in this review on the basis of the recent results reported mainly from our laboratories. Fullerenes act as photo-sensitizing electron acceptors with respect to a wide
[...] Read more.
Photosensitized electron-transfer processes of fullerenes hybridized with electron donating or other electron accepting molecules have been surveyed in this review on the basis of the recent results reported mainly from our laboratories. Fullerenes act as photo-sensitizing electron acceptors with respect to a wide variety of electron donors; in addition, fullerenes in the ground state also act as good electron acceptors in the presence of light-absorbing electron donors such as porphyrins. With single-wall carbon nanotubes (SWCNTs), the photoexcited fullerenes act as electron acceptor. In the case of triple fullerene/porphyrin/SWCNT architectures, the photoexcited porphyrins act as electron donors toward the fullerene and SWCNT. These mechanisms are rationalized with the molecular orbital considerations performed for these huge supramolecules. For the confirmation of the electron transfer processes, transient absorption methods have been used, in addition to time-resolved fluorescence spectral measurements. The kinetic data obtained in solution are found to be quite useful to predict the efficiencies of photovoltaic cells. Full article
(This article belongs to the Special Issue Fullerene Chemistry)

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