Abstract
The hydrothermal synthesis and structural characterization of new trivalent rare‐earth germanates, Na4[(Y1–aLna)2Ge4O13] (Ln = Eu, Tb, or Yb and Er; a = 0.05, 0.1) and Na4[(Yb0.9Er0.1)2Ge4O13] are reported. The structure of these solids was solved by single‐crystal X‐ray diffraction (150 K). The materials crystallize in the orthorhombic non‐centrosymmetric Pna21 space group, and exhibit a framework comprising unprecedented anionic tetrameric [Ge4O13]10– units, tetrameric units of {GeO4} tetrahedra, and isolated dimeric units encompassing two distinct distorted {REO6} octahedra. These rare‐earth germanates feature interesting photoluminescence properties in the visible and near‐infrared spectral regions. Eu3+ photoluminescence confirms the presence of two distinct rare‐earth sites. Energy transfer between the latter sites is shown for the Yb3+/Er3+ pair, both displaying significant near‐infrared emission. Isomorphous Na4[(Yb0.9Er0.1)2Ge4O13] features up‐conversion emission, an unusual property among rare‐earth crystalline germanates.
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