Theoretical Study of One-Electron Oxidized Mn(III)- and Ni(II)-Salen Complexes: Localized vs Delocalized Ground and Excited States in Solution.

One-electron oxidized Mn(III)- and Ni(II)-salen complexes exhibit unique mixed-valence electronic structures and charge transfer (CT) absorption spectra. We theoretically investigated them to elucidate the reason why the Mn(III)-salen complex takes a localized electronic structure (class II mixed valence compound by Robin-Day classification) and the Ni(II)-analogue has a delocalized one (class III) in solution, where solvation effect was taken into consideration either by the three-dimensional reference interaction site model self-consistent field (3D-RISM-SCF) method or by the mean-field (MF) QM/MM-MD simulation. The geometries of these complexes were optimized by the 3D-RISM-SCF-U-DFT/M06. The vertical excitation energy and the oscillator strength of the first excited state were evaluated by the general multiconfiguration reference quasi-degenerate perturbation theory (GMC-QDPT), including the solvation effect based on either 3D-RISM-SCF- or MF-QM/MM-MD-optimized solvent distribution. The computational results well agree with the experimentally observed absorption spectra and the experimentally proposed electronic structures. The one-electron oxidized Mn(III)-salen complex with a symmetrical salen ligand belongs to the class II, as experimentally reported, in which the excitation from the phenolate anion to the phenoxyl radical moiety occurs. In contrast, the one-electron oxidized Ni(II)-salen complex belongs to the class III, in which the excitation occurs from the doubly occupied delocalized π1 orbital of the salen radical to the singly occupied delocalized π2 orbital; the π1 is a bonding combination of the HOMOs of two phenolate moieties and the π2 is an antibonding combination. Solvation effect is indispensable for correctly describing the mixed-valence character, the geometrical distortion, and the intervalence CT absorption spectra of these complexes. The number of d electrons and the d orbital energy level play crucial roles to provide the localization/delocalization character of these complexes.