Multi-Frequency High-Field EPR Study of Iron Centers in Malarial Pigments

The multi-frequency high-field electron paramagnetic resonance (HFEPR) was used to study the magnetic properties of malarial pigment hemozoin and its synthetic analogue, β-hematin. (FeIII−protoporphyrin−IX)2 dimers containing five-coordinate high-spin FeIII, S = 5/2, are the building blocks of these pigments. The fit of EPR spectra that were acquired in an unprecedented wide range of microwave frequencies of 34 and 94 GHz for hemozoin and 27−500 GHz for β-hematin yielded a complete set of intrinsic spin Hamiltonian parameters: D = +5.85(1) cm-1, E = 0, g ⊥ = 1.95(1), g ∥ = 2.00(1). These results point to the existence of largely axial symmetry of the iron environment in the bulk phase of hemozoin and β-hematin.