The Short Series of the Oxygen-Poor Lanthanide Oxide Selenides M10OSe14 with M = La–Nd

Single crystals and phase pure samples of oxygen-poor ternary lanthanide oxide selenides with the composition M10OSe14 (M = La–Nd; tetragonal, I41/acd; a = 1592.0–1559.8 pm, c = 2106.5–2062.9 pm) could be obtained by reacting the corresponding metals, selenium and selenium dioxide as oxygen source. Their crystal structures are isotypic with Pr10OS14 and thus contain isolated [OM4]10+ tetrahedra (d(O2––M3+) = 243–248 pm) embedded in a complex anionic {[M6Se14]10–} lanthanide selenide matrix (d(M3+–Se2–) = 288–358 pm). All three crystallographically independent M3+ cations exhibit eight contacts to chalcogenide anions (O2– and/or Se2–) resulting in the formation of bicapped trigonal prismatic coordination polyhedra. The optical band gaps of the oxide selenides M10OSe14 amount to values between 1.89 and 2.04 eV indicating wide band-gap semiconductors.