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Polyoxometalate (POM) cluster anions are shown to serve as covalently coordinated ligands for anatase‐TiO2 nanocrystals, giving isolable assemblies uniquely positioned between molecular macroanions and traditional colloidal nanoparticles. Na+ salts of the water‐soluble polyanionic structures are obtained by reacting amorphous TiO2 with the 1 nm lacunary ion, Na7[α‐XW11O39] (X=P5+), at 170 °C, after...
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