Here we provide evidence that the formation of PuO₂ nanoparticles from oxidized Pu^VI under alkaline conditions proceeds through the formation of an intermediate Pu^V solid phase, similar to NH₄PuO₂CO₃, which is stable over a period of several months. For the first time, state‐of‐the‐art experiments at Pu M₄ and at L₃ absorption edges combined with theoretical calculations unambiguously allow to determine the oxidation state and the local structure of this intermediate phase.

The exotic “Asian Lantern” heterometallic cage silsesquioxane [(PhSiO_1.5)₂₀(FeO_1.5)₆(NaO_0.5)₈(n-BuOH)_9.6(C₇H₈)] (I) was obtained and characterized by X-ray diffraction, EXAFS, topological analyses and DFT calculation.