Experimentally Assessing the Electronic Structure and Spin-State Energetics in MnFe Dimers Using 1s3p Resonant Inelastic X-ray Scattering

The synergistic interaction between Mn and Fe centers is investigated via a comprehensive analysis of full 1s3p resonant inelastic X-ray scattering (RIXS) planes at both the Fe and Mn K-edges in a series of homo- and heterometallic molecular systems. Deconvolution of the experimental two-dimensional 1s3p RIXS maps provides insights into the modulation of metal-ligand covalency and variations in the metal multiplet structure induced by subtle electronic structural differences imposed by the presence of the second metal. These modulations in the electronic structure are key toward understanding the reactivity of biological systems with active sites that require heterometallic centers, including MnFe purple acid phosphatases and MnFe ribonucleotide reductases. Herein, we demonstrate the capabilities of 1s3p RIXS to provide information on the excited state energetics in both element- and spin-selective fashion. The contributing excited states are identified and isolated by their multiplicity and π- and σ-contributions, building a conceptual bridge between the electronic structures of metal centers and their reactivity. The ability of the presented 1s3p RIXS methodology to address fundamental questions in transition metal catalysis reactivity is highlighted.