Room‐Temperature Oxidation of Thulium‐Metal Nanoparticles to the Thulium Oxocluster [Tm5O(OiPr)13]

Abstract Zerovalent thulium nanoparticles (2.2±0.3 nm in size) are used as the starting material to prepare single crystals of the thulium oxocluster [Tm 5 O(O i Pr) 13 ]. The reaction is performed by controlled oxidation of the Tm(0) nanoparticles at room temperature (25°C) in isopropanol. The pentanuclear oxocluster contains a non‐charged molecular unit with a central Tm 5 O core and five μ 1 ‐, four μ 2 ‐, and four μ 3 ‐bridging (O i Pr) − ligands. Single‐crystal structure analysis ( P 2 1 /n , a =1247.7(6), b =2146.2(15), c =2056.6(9) pm, β =93.23(1)°) and infrared spectroscopy confirm the oxidation of HO i Pr with formation of H 2 and (O i Pr) − . Temperature‐dependent measurements show antiferromagnetic coupling. Such a polynuclear [ Ln 5 O(O i Pr) 13 ] oxocluster ( Ln : lanthanide) is prepared with thulium‐metal nanoparticles as a starting material for the first time and points to the suitability of reactive rare‐earth metal nanoparticles as starting materials.