Study of the Structure and Spectral Properties of Radical Anions of Zn Complexes of Porphyrins by the Method of Density Functional Theory

摘要

The structure, solvation energies, and electronic absorption spectra of possible products of the reaction of Zn porphin (Zn-P) with metallic sodium are calculated using methods of density functional theory. Calculated solvation energies of free and bound ions make it possible to assume that, in commonly used aprotic solvents, reduction products occur as [Na~(+) (centre dot) Zn-P~(-)]_(N, C_(m)) anion-cation contact pairs, with Na~(+) lying along either the NN or C_(m)C_(m) axis. This conclusion is consistent with results of calculations of electronic absorption spectra and of modeling of spectral manifestations of the electron photodetachment in frozen matrices.