Theoretical study on the highly chlorinated smaller fullerenes of C30–C48

Stimulated by recent preparation and characterization of the first C50Cl10 fullerene derivative with five fused pentagons and four novel chlorinated fullerene derivatives, C54Cl8, C56Cl12, C66Cl6 and C66Cl10 with the triple sequentially fused pentagons, 30 exohedral chlorine derivatives of small fullerenes C30–C48 have been reported here. The geometrical structures and electronic properties of them are studied using density functional theory (DFT) at the B3LYP/6-31G∗ level. The HOMO–LUMO gaps, reaction energies, and aromaticities commonly used for chemical viability of chlorinated small fullerenes were compared with these values of the two most stable fullerene derivatives C50Cl10 and C60Cl30. The presented data reveal that many unknown fullerene derivatives are stable molecules, especially for C32Cl20 (3, D3d), C36Cl18 (13, D3h), and C40Cl16 (40, Td). The stable behavior of them resembles the well-known C50Cl10. It is quite possible that they can be synthesized experimentally in the solid after C50.