Functionalization of pentagon–pentagon edges of fullerenes by cyclic polysulfides: A DFT study

• Published in: The Journal of physics and chemistry of solids 2016-05, Vol.92, p.26-31
• Main Authors: Anafcheh, Maryam, Khodadadi, Zahra, Ektefa, Fatemeh, Ghafouri, Reza
• Format: Article
• Language: English
• Subjects: A. Fullerenes; C. Ab initio calculations
• ISSN: 0022-3697; 1879-2553
• DOI: 10.1016/j.jpcs.2015.12.004

We have performed a computational study to investigate the cyclosulfurization of the pentagon–pentagon (p–p) junctions in the non-IPR fullerenes C60(D3) and C70(C2v), and also Stone-Wales defective C60 fullerene. Our results indicate the exothermic character of cyclosulfurization processes which can be related to the increase of pyramidalization angle (spherical excesses) and p characters of natural hybrid orbitals of C atoms at the p–p junctions. In fact these lead to the structural strain relief and stability of the cyclosulfurization derivatives of the non-IPR fullerenes. Moreover, the cyclosulfurization reaction of p–p bonds on the C70(C2v) is more energetically favorable than that of C60(D3), due to the higher curvature of carbon sites and the larger values of the p characters of natural hybrid orbitals in the C70(C2v). On the other hand, localization of the excess electrons on the C atoms at the p–p junctions leads to the low tendency of the charged non-IPR fullerenes to cyclosulfurization process. The desulfurization pathway of the exohedral derivatives of C70(C2v) indicates that it is energetically unfavorable for the functionalized fullerenes to break into individual fullerene and sulfur molecules. HOMO–LUMO gaps almost are independent of the number of pentathiepin rings while sensitive to the type of parent fullerene. Cyclosulfurization of the Non-IPR Fullerenes. [Display omitted] •Cyclosulfurization of pentagon–pentagon junctions have exothermic character.•Cyclosulfurization of p–p bonds on the C70 (C2v) is more favorable than C60(D3).•Localization of electrons on p–p bonds leads to the low tendency of non-IPR fullerenes.•Desulfurization of functionalized fullerenes is energetically unfavorable.•HOMO–LUMO gaps sensitive to the type of parent fullerene.