La 26 Ge 19 M 5 O 5 (M = Ag, Cu): Rare-Earth Metal Suboxide Superconductors with [La 18 O 5 ] Cluster Units.

Herein we report two reduced rare-earth metal-based superconductors, La 26 Ge 19 M 5 O 5 (M = Ag, Cu), that feature an unprecedented [La 18 O 5 ] cluster composed of five oxygen-centered [La 6 O] octahedra condensed through shared faces and capped with [Ge 4 ] butterfly rings. The structure, determined by single-crystal X-ray diffraction, crystallizes in a tetragonal space group ( P 4/ nmm ), with a = 15.508(2) Å and c = 11.238(2) Å. Resistivity and magnetic susceptibility measurements show onsets of superconductivity at T c = 5.4 and 6.4 K for the Ag and Cu compounds, respectively. Applying high pressures, up to 1.3 GPa, results in increased superconducting transition temperatures ( T c = 6.8 K for Ag and 7.2 K for Cu compounds), with no sign of saturation.