High-frequency and -field electron paramagnetic resonance of high-spin manganese(III) in tetrapyrrole complexes

High-field and -frequency electron paramagnetic resonance (HFEPR) spectroscopy has been used to study three complexes of high spin Manganese(III), 3d 4, S=2. The complexes studied were tetraphenylporphyrinatomanganese(III) chloride (MnTPPCl), phthalocyanatomanganese(III) chloride (MnPcCl), and (8,12-diethyl-2,3,7,13,17,18-hexamethylcorrolato)manganese(III) (MnCor). We demonstrate the ability to obtain both field-oriented (single-crystal like) spectra and true powder pattern HFEPR spectra of solid samples. The latter are obtained by immobilizing the powder, either in an n-eicosane mull or KBr pellet. We can also obtain frozen solution HFEPR spectra with good signal-to-noise, and yielding the expected true powder pattern. Frozen solution spectra are described for MnTPPCl in 2:3 (v/v) toluene/CH 2Cl 2 solution and for MnCor in neat pyridine (py) solution. All of the HFEPR spectra have been fully analyzed using spectral simulation software and a complete set of spin Hamiltonian parameters has been determined for each complex in each medium. Both porphyrinic complexes (MnTPPCl and MnPcCl) are rigorously axial systems, with similar axial zero-field splitting (zfs): D≈−2.3 cm −1, and g values quite close to 2.00. In contrast, the corrole complex, MnCor, exhibits slightly larger magnitude, rhombic zfs: D≈−2.6 cm −1, | E|≈0.015 cm −1, also with g values quite close to 2.00. These results are discussed in terms of the molecular structures of these complexes and their electronic structure. We propose that there is a significant mixing of the triplet ( S=1) excited state with the quintet ( S=2) ground state in Mn(III) complexes with porphyrinic ligands, which is even more pronounced for corroles.