Jump to main content
Jump to site search


Theoretical study of one-electron-oxidized salen complexes of group 7 (Mn(III), Tc(III), and Re(III)) and group 10 metals (Ni(II), Pd(II), and Pt(II)) with the 3D-RISM-GMC-QDPT method: localized vs. delocalized ground and excited states in solution

Author affiliations

Abstract

One-electron oxidized salen complexes of Mn(III) and Ni(II) were recently reported to be unique mixed-valence compounds. Their electronic structures are sensitive to the salen ligand and solvation. We systematically investigated a series of one-electron oxidized salen complexes of group 7 metals (Mn(III), Tc(III), and Re(III)) and their group 10 analogues (Ni(II), Pd(II), and Pt(II)) using the general multi-configuration reference quasi-degenerate perturbation theory (GMC-QDPT) which was combined with the three-dimensional reference interaction site model self-consistent field theory (3D-RISM-SCF) to incorporate the solvation effect. The calculated absorption spectra and electronic structures agree with the experimental observation. The one-electron oxidized salen complexes of group 10 metals with a symmetrical salen ligand have a delocalized electronic structure belonging to class III (Robin–Day classification) in weakly polar solvents. The tendency for taking a delocalized electronic structure increases in the order Pd(II) < Ni(II) < Pt(II). When the salen ligand is asymmetrical, the one-electron oxidized complexes have a localized electronic structure belonging to class II. The group 7 analogues of Mn(III) and Tc(III) have a localized electronic structure belonging to class II even in weakly polar solvents and even with a symmetrical salen ligand. However, the one-electron oxidized Re(III) complex has no mixed-valence nature because one-electron oxidation occurs on the Re center. Theoretical study shows that the solvation effect plays a crucial role in determining the mixed-valence character, class II or III, and thereby its incorporation in the calculation is indispensable for correctly describing geometries, electronic structures, and the inter-valence absorption spectra of these complexes. The d orbital energy is one of the most important factors for determining the localization/delocalization electronic structures in these complexes. Detailed discussion of these factors is presented.

Graphical abstract: Theoretical study of one-electron-oxidized salen complexes of group 7 (Mn(iii), Tc(iii), and Re(iii)) and group 10 metals (Ni(ii), Pd(ii), and Pt(ii)) with the 3D-RISM-GMC-QDPT method: localized vs. delocalized ground and excited states in solution

Back to tab navigation

Supplementary files

Publication details

The article was received on 06 May 2017, accepted on 30 May 2017 and first published on 30 May 2017


Article type: Paper
DOI: 10.1039/C7CP02992F
Citation: Phys. Chem. Chem. Phys., 2017, Advance Article
  •   Request permissions

    Theoretical study of one-electron-oxidized salen complexes of group 7 (Mn(III), Tc(III), and Re(III)) and group 10 metals (Ni(II), Pd(II), and Pt(II)) with the 3D-RISM-GMC-QDPT method: localized vs. delocalized ground and excited states in solution

    S. Aono, M. Nakagaki and S. Sakaki, Phys. Chem. Chem. Phys., 2017, Advance Article , DOI: 10.1039/C7CP02992F

Search articles by author

Spotlight

Advertisements