Assembly of cerium(III)-stabilized polyoxotungstate nanoclusters with SeO₃^2-/TeO₃^2- templates. From single polyoxoanions to inorganic hollow spheres in dilute solution

A versatile one-pot strategy was employed to synthesize three cerium(III)-stabilized polyoxotungstates nanoclusters by combining cerium linkers and SeO₃^2-/TeO₃^2- heteroanion templates: K₃₂Na₁₆[{(XO₃)W₁₀O₃₄}₈{Ce₈(H₂O)₂₀}(WO₂)₄-(W₄O₁₂)].n H₂O [X=Se, n=81 (1); X=Te, n=114 (2)] and K₁₂Na₂₂[{(SeO₃)W₁₀O₃₄}₈{Ce₈(H₂O)₂₀}(WO₂)₄-{(W₄O₆)Ce₄(H₂O)₁₄(SeO₃)₄(NO₃)₂}] . 79 H₂O (3), which are the first lanthanide-containing polyoxotungstates with selenium or tellurium heteroatoms. The three clusters were characterized by single-crystal X-ray structure analysis, IR spectroscopy, thermogravimetric/differential thermal analysis, UV/Vis spectroscopy, ESI-MS, and X-ray photoelectron spectroscopy. Their electrochemical, photoluminescence, and magnetic properties were investigated. Their behavior in solution was studied by transmission electron microscopy, which showed that their single polyoxoanions assemble into intact, uniform-sized, purely inorganic hollow spheres in dilute water/acetone solution. (Copyright copyright 2013 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)