Infrared spectra and electronic configuration of anionic forms of nickel and cobalt octaethylporphin in the solid phase

On the basis of an investigation of IR spectra, electronic configurations have been established for the monoanions of Ni and Co octaethylporphin and the dianion of Ni octaethylporphin in the solid phase; characteristic features have been revealed in the effects on the IR spectra of metalloporphyrins from occupancy of their vacant \({\text{d}}_{{\text{z}}^{\text{2}} }\) and \(d_{x^2 - y^2 }\) orbitals by additional electrons. It has been shown that interaction of the anions with alkali metal countercations may lead (depending on the electronic configuration of the anion and the type of cation) to activation of bands of composite vibrations in the IR spectrum. It has been found that the monoanions of Ni octaethylporphin are capable of existing in d- and π-electronic configurations, depending on the phase state (solution or film) and the crystal modification in the solid phase.