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

Abstract

AbstractZerovalent thulium nanoparticles (2.2±0.3 nm in size) are used as the starting material to prepare single crystals of the thulium oxocluster [Tm5O(OiPr)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 Tm5O core and five μ1‐, four μ2‐, and four μ3‐bridging (OiPr)− ligands. Single‐crystal structure analysis (P21/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 HOiPr with formation of H2 and (OiPr)−. Temperature‐dependent measurements show antiferromagnetic coupling. Such a polynuclear [Ln5O(OiPr)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.