Articles producció científica> Química Física i Inorgànica

Small endohedral metallofullerenes: exploration of the structure and growth mechanism in the Ti@C-2n (2n=26-50) family

  • Identification data

    Identifier: imarina:9297439
  • Authors:

    Mulet-Gas, Marc
    Abella, Laura
    Dunk, Paul W.
    Rodriguez-Fortea, Antonio
    Kroto, Harold W.
    Poblet, Josep M.
  • Others:

    Author, as appears in the article.: Mulet-Gas, Marc; Abella, Laura; Dunk, Paul W.; Rodriguez-Fortea, Antonio; Kroto, Harold W.; Poblet, Josep M.;
    Department: Química Física i Inorgànica
    URV's Author/s: Abella Guzman, Laura / Poblet Rius, Josep Maria / Rodríguez Fortea, Antonio
    Keywords: Stability Rule Reactivity Initio molecular-dynamics Graphite Fullerenes C-60 Approximation
    Abstract: The formation of the smallest fullerene, C-28, was recently reported using gas phase experiments combined with high-resolution FT-ICR mass spectrometry. An internally located group IV metal stabilizes the highly strained non-IPR C-28 cage by charge transfer (IPR = isolated pentagon rule). Ti@C-44 also appeared as a prominent peak in the mass spectra, and U@C-28 was demonstrated to form by a bottom-up growth mechanism. We report here a computational analysis using standard DFT calculations and Car-Parrinello MD simulations for the family of the titled compounds, aiming to identify the optimal cage for each endohedral fullerene and to unravel key aspects of the intriguing growth mechanisms of fullerenes. We show that all the optimal isomers from C-26 to C-50 are linked by a simple C-2 insertion, with the exception of a few carbon cages that require an additional C-2 rearrangement. The ingestion of a C-2 unit is always an exergonic/exothermic process that can occur through a rather simple mechanism, with the most energetically demanding step corresponding to the closure of the carbon cage. The large formation abundance observed in mass spectra for Ti@C-28 and Ti@C-44 can be explained by the special electronic properties of these cages and their higher relative stabilities with respect to C-2 reactivity. We further verify that extrusion of C atoms from an already closed fullerene is much more energetically demanding than forming the fullerene by a bottom-up mechanism. Independent of the formation mechanism, the present investigations strongly support that, among all the possible isomers, the most stable, smaller non-IPR carbon cages are formed, a conclusion that is also valid for medium and large cages.
    Thematic Areas: Química Materiais Interdisciplinar General chemistry Farmacia Ciências biológicas iii Ciências biológicas i Chemistry, multidisciplinary Chemistry (miscellaneous) Chemistry (all) Astronomia / física
    licence for use: https://creativecommons.org/licenses/by/3.0/es/
    Author's mail: laura.abella@urv.cat josepmaria.poblet@urv.cat antonio.rodriguezf@urv.cat
    Author identifier: 0000-0002-4533-0623 0000-0001-5884-5629
    Record's date: 2024-07-20
    Papper version: info:eu-repo/semantics/publishedVersion
    Link to the original source: https://pubs.rsc.org/en/content/articlelanding/2015/sc/c4sc02268h
    Licence document URL: http://repositori.urv.cat/ca/proteccio-de-dades/
    Papper original source: Chemical Science. 6 (1): 675-686
    APA: Mulet-Gas, Marc; Abella, Laura; Dunk, Paul W.; Rodriguez-Fortea, Antonio; Kroto, Harold W.; Poblet, Josep M.; (2015). Small endohedral metallofullerenes: exploration of the structure and growth mechanism in the Ti@C-2n (2n=26-50) family. Chemical Science, 6(1), 675-686. DOI: 10.1039/c4sc02268h
    Article's DOI: 10.1039/c4sc02268h
    Entity: Universitat Rovira i Virgili
    Journal publication year: 2015
    Publication Type: Journal Publications
  • Keywords:

    Chemistry (Miscellaneous),Chemistry, Multidisciplinary
    Stability
    Rule
    Reactivity
    Initio molecular-dynamics
    Graphite
    Fullerenes
    C-60
    Approximation
    Química
    Materiais
    Interdisciplinar
    General chemistry
    Farmacia
    Ciências biológicas iii
    Ciências biológicas i
    Chemistry, multidisciplinary
    Chemistry (miscellaneous)
    Chemistry (all)
    Astronomia / física
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