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

High-field and -frequency electron paramagnetic resonance (HFEPR) spectrosc opy has been used to study two complexes of high-spin manganese(III), d(4), S = 2. The complexes studied were (tetraphenylporphyrinato)manganese(III) chloride and (phthalocyanato)manganese(III) chloride. Our previous HFEPR st udy (Goldberg, D. P.; Telser, J.; Krzystek, J.; Montalban, A. G.; Brunel, L .-C.; Barrett, A. G. M.; Hoffman, B. M. J. Ain. Chem. Sec. 1997, 119, 8722- 8723) included results on the porphyrin complex; however, we were unable to obtain true powder pattern HFEPR spectra, as the crystallites oriented in the intense external magnetic field. In this work we are now able to immobi lize the powder, either in an n-eicosane mull or KBr pellet and obtain true powder pattern spectra. These spectra have been fully analyzed using spect ral simulation software, and a complete set of spin Hamiltonian parameters has been determined for each complex. Both complexes are rigorously axial s ystems, with relatively low magnitude zero-field splitting: D approximate t o -2.3 cm(-1) and g values quite close to 2.00. Prior to this work, no expe rimental nor theoretical data exist for the metal-based electronic energy l evels in Mn(III) complexes of porphyrinic ligands. This lack of information is in contrast to other transition metal complexes and is likely due to th e dominance of ligand-based transitions in the absorption spectra of Mn(III ) complexes of this type. We have therefore made use of theoretical values for the electronic energy levels of (phthalocyanato)copper(II), which elect ronically resembles these Mn(III) complexes. This analogy works surprisingl y well in terms of the agreement between the calculated and experimentally determined EPR parameters. These results show a significant mixing of the t riplet (S = I) excited state with the quintet (S = 2) ground state in Mn(II I) complexes with porphyrinic ligands. This is in agreement with the experi mental observation of lower spin ground states in other metalloporphyrinic complexes, such as those of Fe(II) with S = 1.