Abstract
Very recently, a series of endohedral fullerenes Sc2O@C2n (n = 35-47) were facilely produced. However, only two of them have been further characterized so far. Theoretically, we studied another discandium oxide endohedral fullerene without any characterizations, Sc2O@C84, which is the second most-abundant species in terms of relative heights of all mass spectrum peaks. Two thermodynamically stable isomers with isolated pentagon rule-obeying cages were found, namely, Sc2O@C2v(51575)-C84 and Sc2O@C1(51580)-C84. This is the first case that an endohedral fullerene containing the C2v(51575)-C84 cage acts as the lowest-energy isomer, and it is the first report of a clusterfullerene containing the C1(51580)-C84 cage. The endohedral Sc2O cluster can keep its ideal structure after encapsulation, while both C84 cages have deformed dramatically. Orbital analysis suggests that nucleophilic and oxidization reactions of both isomers should take place on the cage, while regioselectivity of Sc2O@C2v(51575)-C84 and Sc2O@C1(51580)-C84 is different due to their different characteristics of the highest occupied orbital distribution. Two-dimensional electron localization function and Laplacian of electron density maps unambiguously indicate strong electrostatic interactions exist between one scandium atom and the oxygen one. Meanwhile, overlaps of occupied metal atom orbitals and the cage ones along with Mayer bond order analysis identify that covalent interactions between a scandium atom and each C84 cage cannot be neglected. At last, (13)C NMR, UV-vis-NIR, and IR spectra of both Sc2O@C84 isomers were simulated theoretically. Because of their structural difference, all spectra between two isomers are significantly divergent. Consequently, these spectra are helpful to distinguish Sc2O@C2v(51575)-C84 and Sc2O@C1(51580)-C84 in further experimental characterizations.
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Disclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.