Synthesis and Crystal Structure of the Europium(II) Hydride Oxide Iodide Eu5H2O2I4 Showing Blue-Green Luminescence.

As the first europium(II) hydride oxide iodide, dark red single crystals of Eu5H2O2I4 could be synthesized from oxygen-contaminated mixtures of EuH2 and EuI2. Its orthorhombic crystal structure (a = 1636.97(9) pm, b = 1369.54(8) pm, c = 604.36(4) pm, Z = 4) was determined via single-crystal X-ray diffraction in the space group Cmcm. Anion-centred tetrahedra [HEu4]7+ and [OEu4]6+ serve as central building blocks interconnected via common edges to infinite ribbons parallel to the c axis. These ribbons consist of four trans-edge connected (Eu2+)4 tetrahedra as repetition unit, two H--centred ones in the inner part, and two O2--centred ones representing the outer sides. They are positively charged, according to ∞1{[Eu5H2O2]4+}, to become interconnected and charge-balanced by iodide anions. Upon excitation with UV light, the compound shows blue-green luminescence with the shortest Eu2+ emission wavelength ever observed for a hydride derivative, peaking at 463 nm. The magnetic susceptibility of Eu5H2O2I4 follows the Curie-Weiss law down to 100 K, and exhibits a ferromagnetic ordering transition at about 10 K.

Borate Hydrides as a New Material Class: Structure, Computational Studies, and Spectroscopic Investigations on Sr5 (BO3 )3 H and Sr5 (11 BO3 )3 D.

The unprecedented borate hydride Sr5 (BO3 )3 H and deuteride Sr5 (11 BO3 )3 D crystallizing in an apatite-related structure are reported. Despite the presence of hydride anions, the compound decomposes only slowly in air. Doped with Eu2+ , it shows broad-band orange-red emission under violet excitation owing to the 4f6 5d-4f7 transition of Eu2+ . The observed 1 H NMR chemical shift is in good agreement with previously reported 1 H chemical shifts of ionic metal hydrides as well as with quantum chemical calculations and very different from 1 H chemical shifts usually found for hydroxide ions in similar materials. FTIR and Raman spectroscopy of different samples containing 1 H, 2 H, nat B, and 11 B combined with calculations unambiguously prove the absence of hydroxide ions and the sole incorporation of hydride ions into the borate. The orange-red emission obtained by doping with Eu2+ shows that the new compound class might be a promising host material for optical applications.