Substituent Effect in the Cation Radicals of Monosubstituted Benzenes.

In 30 monosubstituted benzene cation radicals, studied at the ωB97XD/aug-cc-pVTZ level, the phenyl rings usually adopt a compressed form, but a differently compressed form-equivalent to an elongated one-may coexist. The computational and literature ionization potentials are well correlated. The geometrical and magnetic aromaticity, estimated using HOMA and NICS indices, show the systems to be structurally aromatic but magnetically antiaromatic or only weakly aromatic. The partial charge is split between the substituent and ring and varies the most at C(ipso). In the ring, the spin is 70%, concentrated equally at the C(ipso) and C(p) atoms. The sEDA() and pEDA() descriptors of the substituent effect in cation radicals, respectively, were determined. In cation radicals, the substituent effect on the σ-electron system is like that in the ground state. The effect on the π-electron systems is long-range, and its propagation in the radical quinone-like ring is unlike that in the neutral molecules. The pEDA() descriptor correlates well with the partial spin at C(ipso) and C(p) and weakly with the HOMA() index. The correlation of the spin at the ring π-electron system and the pEDA() descriptor shows that the electron charge supplied to the ring π-electron system and the spin flow oppositely.