Calculation of the structure and vibrational states for anionic forms of Co-, Ni-, and Cu-porphines

The structure and vibrations of neutral porphine metal complexes (Me-P, Me = Co, Ni, Cu) and their d-anionic forms with an additional electron localized in vacant $d_x^2 -_y^2 -$ and $d_z^2$-orbitals are compared based on calculations by a DFT method. It is shown that such electron population causes a significant increase of the electronic charge on the macrocycle rather than on the Me atom and is accompanied by a considerable redistribution of π- and σ-electron densities (ρ_π ρ_σ). A predominant gain of ρ_π (0.49e) is found for the monoanion of Co-P (Co-P^–, $d_z^2$-monoanion); of ρ_σ (0.6e), for Ni-P^–( $d_x^2 -_y^2 -$monoanion). These features are reflected in both the structure of the anions and the behavior of their vibrational frequencies. The greatest frequency shifts among IR active modes when populating the $d_z^2$- and $d_x^2 -_y^2 -$orbitals occur for out-of-plane vibrations (>30 cm^–1) and in-plane modes (34–46 cm^–1) involving MeN- and C_αC_m-bonds, respectively. Abnormally large frequency lowering is found for B_1g-type modes (active in the resonance Raman spectrum) involving mainly C_αC_m-, C_βC_β-, C_αC_β-, and MeN-bonds. This is related to a change in the d_π-e_g interaction strength during such vibrations that contributes to a decrease in the corresponding force constants.