Mn^II/III and Ce^III/IV Units Supported on an Octahedral Molecular Nanoparticle of CeO₂

The preparation of three new heterometallic clusters [Ce₆Mn₁₂O₁₇(O₂CPh)₂₆] (1), [Ce₁₀Mn₁₄O₂₄(O₂CPh)₃₂] (2), and [Ce₂₃Mn₂₀O₄₈(OH)₂(tbb)₄₆(H₂O)₄](NO₃)₂ (3; tbb^- = 4-^tBu-benzoate) is reported. They all possess unprecedented structures with a common feature being the presence of an octahedral Ce^IV-oxo core: a Ce₆ in 1, two edge-fused Ce₆ giving a Ce₁₀ bioctahedron in 2, or a larger Ce₁₉ octahedron in 3. Complex 1 is the first Ce₆ cluster with a central μ₆-O^2-. 2 and the cation of 3 are molecular nanoparticles of CeO₂ (ceria) because they possess the fluorite structure of bulk ceria and are thus ultrasmall ceria nanoparticles in molecular form. The {Ce₁₉O₃₂} octahedral subunit of the cation of 3 had been predicted from density functional theory studies to be one of the stable fragments of the CeO₂ lattice, but has never been previously synthesized in molecular chemistry. Around the Ce/O core of 1-3 is an incomplete monolayer of Mn ions disposed as four Mn₃, two Mn₇, and four Mn₅ units, respectively. This represents a clear structural similarity with composite (phase-separated) CeO₂/MnO mixtures where at high Ce:Mn ratios the Mn atoms segregate on the surface of CeO₂ phases. Variable-temperature dc and ac magnetic susceptibility studies have revealed S = 2, S = ¹/₂, and S = ³/₂ ground states for 1-3, respectively. Fitting of the 5.0-300 K dc data for 1 to a two-J model for an asymmetrical V-shaped Mn₃ unit with no interaction between the end Mn^III ions gave an excellent fit with the following values: J₁ = 5.2(3) cm^-1, J₂ = -7.4(3) cm^-1, and g = 1.96(2).