The electronic properties of three popular high spin complexes [TM(acac), TM = Cr, Mn, and Fe] revisited: an experimental and theoretical study.

The occupied and unoccupied electronic structures of three high spin TM(acac) (TM = Cr, Mn, and Fe) complexes (I, II, and III, respectively) were studied by revisiting their literature vapour-phase He(i) and, when available, He(ii) photoemission (PE) spectra and by means of original near-edge X-ray absorption fine structure (NEXAFS) spectroscopic data recorded at the O K-edge (K-edge) and TM L-edges (L-edges). The assignments of the vapour-phase He(i)/He(ii) PE spectra were guided by the results of spin-unrestricted non-relativistic Slater transition state calculations, while the K-edge and L-edge spectroscopic pieces of evidence were analysed by exploiting the results of spin-unrestricted scalar-relativistic time-dependent density functional theory (DFT) and DFT/ROCIS calculations, respectively. Although the actual symmetry (D, in the absence of any Jahn-Teller distortion) of the title molecules allowed an extensive mixing between TM t-like and e-like atomic orbitals, the use of the Nalewajski-Mrozek TM-O bond multiplicity index combined with a thorough analysis of the ground state (GS) outcomes allowed the assessment of the TM-O bond weakening associated with the progressive TM 3d-based e-like orbital filling. The experimental information provided by K-edge spectra was rather poor; nevertheless, the combined use of symmetry, orbitals and spectra allowed us (i) to rationalise minor differences characterizing spectral features along the series, (ii) to quantify the contribution provided by the ligand-to-metal-charge-transfer (LMCT) excitations to the different spectral features, and (iii) to recognize the t-/e-like nature of the TM 3d-based orbitals involved in LMCT transitions. As far as the L-edge spectra and the DFT/ROCIS results were concerned, the lowest lying IIIL spectral features included states having either the GS spin multiplicity (S(I) = 3/2, S(II) = 2) or, at higher excitation energies (EEs), states with ΔS = ±1. In contrast to that, only states with ΔS = 0, -1 significantly contributed to the IIIL spectral pattern. Along the whole series, the L higher EE side was systematically characterized by states involving 2p → π MLCT excitations; as such, coupled-single excitations with ΔS = 0 were involved in I and II, while single MLCT 2p → π transitions with ΔS = -1 were involved in III.