Theoretical studies on the heats of formation and the interactions among the difluoroamino groups in polydifluoroaminocubanes.

The heats of formation (HOFs) were calculated for a series of polydifluoroaminocubanes by using density functional theory (DFT), Hartree-Fock, and MP2 method with 6-31G basis set as well as semiempirical methods. The cubane skeleton was not broken in the process of designing isodesmic reactions; i.e., the cubane skeleton was chosen for a reference compound. The contribution of difluoroamino group to the heat of formation deviates from group additivity. The semiempirical MO (MNDO, AM1, and PM3) methods did not produce accurate and reliable results for the HOFs of the title compounds. The relationship between HOFs and molecular structures was discussed. It was found that the HOFs decreased dramatically initially and then gradually with each difluoroamino group attached to the cubane skeleton. The distance between difluoroamino groups influences the values of HOFs. The interacting energies of polydifluoroaminocubanes are in the range 14-20 kJ/mol. The interaction of neighbor difluoroamino groups discords with the group additivity. The average interaction energy between the nearest-neighbor NF(2) group in the most stable conformer of octadifluoroaminocubane is 13.94 kJ/mol at the B3LYP/6-31G level. The NF(2) group can rotate freely around the C-N bond. The relative stability of the title compounds was accessed on the basis of the calculated HOFs, the energy gaps between the frontier orbitals, and the bond order of C-NF(2). These results provide basic information for the molecular design of novel high energetic density materials.