Computational and Chemical Analysis of the Oxygen Atom Transfer Process of a Dioxo–Molybdenum Complex Incorporated into a Modified UiO-67 (Zr/Ti)

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.