Density functional study of 2-[(R-Phenyl)amine]-1,4-naphthalenediones

The molecular and electronic structures of a series of 2-[(R-phenyl)amine]-1,4-naphthalenediones (R= m-Me, p-Me, m-Et, p-CF3, p-Hex, p-Et, m-F, m-Cl, p-OMe, p-COMe, p-Bu, m-COOH, p-Cl, p-COOH, p-Br, m-NO2, m-CN, and p-NO2) and their anions are investigated in the framework of density functional theory. The calculations are of all-electron type using a double zeta valence polarization basis set optimized for density functional theory methods. The theoretical study shows that all compounds are nonplanar. The nonplanarity can be rationalized in terms of occupied pi orbitals. A linear correlation between the measured half- wave potentials and the calculated gas- phase electron affinities is found. It holds for local as well as generalized gradient corrected functionals. Structural parameters, harmonic vibrational frequencies, and adiabatic and vertical electron affinities as well as orbital and spin density plots of the studied compounds are presented.