Abstract
Electron spin echo envelope modulation (ESEEM) studies were utilized to characterize the coupling between protons of axially bound pyrazole ligands (PzH) and the unpaired electron of low-spin tetraphenylporphyrinatoiron(III) chloride. Samples were prepared in mixed-solvent glasses to maximize the resolution of the electron paramagnetic resonance (EPR) signals. X-band two-pulse ESEEM experiments at 4.2 K in deuterated solvent glasses demonstrated that this coupling results in 0.2−0.7 MHz shifts of the να + νβ proton sum combination peak from twice the Larmor frequency. These shifts have been investigated across most of the EPR absorption spectrum of [TPPFe(PzH)2]+Cl-. Two-pulse ESEEM spectra were simulated at different magnetic field positions. Combination peaks were observed from both distant protons (DP) (β-pyrrole, ortho-phenyl, and β-pyrazole) and near protons (NP) (α-H of the pyrazole ligands). For the simulations, the orientation of the nearest four protons of the pyrazole ligands with respect to the...
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