Computational and Chemical Analysis of the Oxygen Atom Transfer Process of a Dioxo-Molybdenum Complex Incorporated...

In the present work, a combined theoretical-experimental approach was employed to elucidate the structure of a modified UiO-67 (Zr/Ti) MOF functionalized with MoO₂Cl₂ through a three-step process and to propose a detailed mechanism for the oxygen atom transfer reaction. Experimental characterization techniques (X-ray diffraction, X-ray photoelectron spectroscopy, and electron paramagnetic resonance (EPR)) were integrated with periodic and cluster-based density functional theory calculations to validate the synthesis and to model the catalytic behavior. EPR data confirmed the formation of Mo^(V) species during the catalytic cycle, supporting the intermediates proposed by theoretical studies. This synergistic strategy enabled a deep understanding of both the synthesis process and the catalyst's function, demonstrating how theory-guided design and experimental validation can drive the development of next-generation MOFs with tunable reactivity and scalable application potential.