화학공학소재연구정보센터
Inorganic Chemistry, Vol.52, No.5, 2372-2387, 2013
Electronic Structure and Spectroscopic Properties of Mononuclear Manganese(III) Schiff Base Complexes: A Systematic Study on [Mn(acen)X] Complexes by EPR, UV/vis, and MCD Spectroscopy (X = Hal, NCS)
The manganese(III) Schiff base complexes [Mn(acen)X] (H(2)acen: N,N'-ethylenebis(acetylacetone)imine, X: I-, Br-, Cl-, NCS-) are considered as model systems for a combined study of the electronic structure using vibrational, UV/vis absorption, parallel-mode electron paramagnetic resonance (EPR) and low-temperature magnetic circular dichroism (MCD) spectroscopy. By variation of the co-ligand X, the influence of the axial ligand field within a given square-pyramidal coordination geometry on the UV/vis, EPR, and MCD spectra of the title compounds is investigated. Between 25000 and 35000 cm(-1), the low-temperature MCD spectra are dominated by two very intense, oppositely signed pseudo-A terms, referred to as "double pseudo-A terms", which change their signs within the [Mn(acen)X] series dependent on the axial ligand X. Based on molecular orbital (MO) and symmetry considerations, these features are assigned to pi(n.b.)(s, a) --> yz, z(2) ligand-to-metal charge transfer transitions. The individual MCD signs are directly determined from the calculated MOs of the [Mn(acen)X] complexes. The observed sign change is explained by an inversion of symmetry among the pi(n.b.)(s, a) donor orbitals which leads to an interchange of the positive and negative pseudo-A terms constituting the "double pseudo-A term".