Comparative theoretical study of three C56 fullerenes, their chlorinated derivatives, and chlorofullerene oxides

Publication date: 1 October 2017 Source:Computational and Theoretical Chemistry, Volume 1117 Author(s): Fuwei Zhang The thermal stabilities and electronic properties of the three C56 fullerenes (#916C56, #864C56, and #913C56), their chlorinated derivatives, and the corresponding chlorofullerene oxides are investigated and compared using density functional theory (DFT) at the B3LYP/6-31G(d) level. #916C56 is the most stable isomer, but #916C56 and #864C56 possess almost degenerate energies (relative total energy 0.03kcal/mol). The three experimentally observed C56 chlorides display the rather high chemical stabilities with the high exothermicities of their chlorination reactions (reaction energy between −38.86 and −48.89kcal/mol), large HOMO-LUMO energy gaps (between 2.69 and 3.24eV), and the aromatic character (nucleus independent chemical shifts between −13.6 and −17.6ppm). Further addition of oxygen atom to the active sites of C56 chlorofullerenes results in the large stabilities of chlorofullerene oxides. Highly exothermic oxidation addition reactions (reaction energy between −83.66 and −87.24kcal/mol) along with large HOMO-LUMO gaps (between 2.82 and 3.38eV) indicate that these three chlorofullerene oxides are stable molecules. Similar to C56 chlorofullerenes, all investigated chlorofullerene oxides also possess aromatic nature. Hence, #864C56Cl12O and #916C56Cl12O like the well-known #913C56Cl10O can be isolated experimentally. The IR spectra have also bee...

Source: Computational and Theoretical Chemistry - August 8, 2017 Category: Chemistry Source Type: research