Spectroscopic characterization of metal ligation in trinuclear iron-μ₃-oxo-based complexes and metal-organic...

The adsorption-based functionalities of porous metal-organic framework (MOF) materials that lead to applications such as catalysis and gas separation rely on specific host-guest interactions often involving the framework metal sites. These interactions are difficult to probe on the molecular level and consequently poorly understood. Conventional X-ray absorption spectroscopy (XAS) methods can provide molecular-level insights but, as the sole method of characterization, often lack the ligand sensitivity required to probe the relevant local metal coordination changes associated with MOF adsorption processes. Here, we investigate a series of trinuclear iron μ₃-oxo-based MOFs under different metal-coordinating guest environments (water, pyridine, propylene, and guest-free) using a multipronged spectroscopy approach, including valence-to-core X-ray emission spectroscopy (vtc-XES) along with conventional XAS and vibrational spectroscopy, in an effort to characterize their local metal site coordination environments, including ligand identity. Closely related iron μ₃-oxo reference complexes with known coordination are characterized as well for comparison to evaluate the ligand diagnostic nature of the combined spectroscopy approach. Density functional theory calculations aid the vtc-XES band assignments and provide insights into the molecular orbital parentage of the vtc transitions. This series of MOFs and complexes illustrates the advantages and limitations of using this combination of complementary techniques for distinguishing subtle differences in framework metal node coordination environments.