Theoretical
Study of One-Electron Oxidized Mn(III)–
and Ni(II)–Salen Complexes: Localized vs Delocalized Ground
and Excited States in Solution
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Abstract
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 π<sub>1</sub> orbital of the salen radical to the singly occupied delocalized
π<sub>2</sub> orbital; the π<sub>1</sub> is a bonding
combination of the HOMOs of two phenolate moieties and the π<sub>2</sub> 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