Reactivity of a Chloride Decorated, Mixed Valent Ce^III/IV₃₈-Oxo Cluster

A cerium-oxo nanocluster capped by chloride ligands, [Ce^IV_38-Ce^IIIO_56-((OH)Cl₅₁(H₂O)₁₁]^10- (n = 1-24), has been isolated from acidic chloride solutions by using potassium counterions. The crystal structure was elucidated using single crystal X-ray diffraction. At the center of the cluster is a {Ce₁₄} core that exhibits the same fluorite-type structure as bulk CeO₂, with eight-coordinate Ce sites bridged by tetrahedral oxo anions. The {Ce₁₄} is further surrounded by a peripheral shell of six tetranuclear {Ce₄} subunits that are located on each of the faces of the core to yield the {Ce₃₈} cluster. The surface of the cluster is capped by 51 bridging/terminal chloride ligands and 11 water molecules; the anionic cluster is charge balanced by potassium counterions that exist in the outer coordination sphere. While assignment of the Ce oxidation state by bond valence summation was ambiguous, Ce L₃-edge X-ray absorption, X-ray photoelectron, and UV-vis-NIR absorption results were consistent with a Ce^III/Ce^IV cluster. Systematic changes in the XANES and UV-vis-NIR absorption spectra over time pointed to reactivity of the cluster upon exposure to air. These changes were examined using single crystal X-ray diffraction, and a clear single-crystal-to-single-crystal transformation was captured; an overall loss of surface-bound chlorides and water molecules as well as new μ₂-OH sites was observed on the cluster surface. This work provides a rare snapshot of metal oxide cluster reactivity. The results may hold implications for understanding the physical and chemical properties of ceria nanoparticles and provide insight into the behavior of other metal-oxo clusters of significant technological and environmental interest.