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Characterization of the UV-Visible absorption spectra of manganese(III) porphyrins with time-dependent density functional theory calculations

Abstract Mn(III) porphyrins display a unique UV–Vis spectrum: compared to the free-base and other metalloporphyrins, a strong red shift of the Soret-band and several extra bands can be observed in their spectra. To understand this behavior, we have recorded the UV–Vis spectra of differently substituted water-soluble Mn(III) porphyrins and conducted extensive theoretical investigations using time-dependent density functional theory. The calculated optical transitions, using the O3LYP functional, agree well with the measured absorption bands. According to the spectral interpretation, the Soret-band involves a mixture of L–L and ligand-to-metal charge transfer excitations, while the Q-bands and the higher-energy bands in the UV region correspond to pure LMCT as well as to ligand to metal-ligand mixed orbital excitations. The impact of the explicit and implicit water solvent on the spectral features is also discussed.