Spectroscopic Signature of Metal-hydroxo and Peroxo Species in K-edge X-ray Absorption Spectra

Metal-dioxygen species are important intermediates formed during dioxygen activations by metalloenzymes in various biological processes, by catalysts in fuel cells, and prior to O₂ evolution by photosystem II. In this work, we focus on manganese-porphyrin complexes using tetramesitylporphyrin ligand (TMP) to explore changes in Mn K-edge X-ray absorption spectroscopy (XAS) associated with the formation of Mn-hydroxide and Mn-O₂ peroxide species. With limited spectroscopic characterization of these compounds, Mn K_β X-ray emission spectroscopy (XES), XAS, density functional theory (DFT), and time-dependent DFT (TD-DFT) analysis will enhance our understanding of their complex electronic structure. We show that the shape of the pre-edge in the K-edge Mn X-ray absorption near-edge structure (XANES) can serve as a spectroscopic signature of the Mn^III-peroxo formation and thus can be used to track the presence of the side-on peroxide as an intermediate in time-resolved or in situ experiments. Our results will help to further summarize the spectroscopic fingerprints for peroxo and hydroxo species, addressing the challenge of identifying the reactive metal species in catalytic reactions.