Abrupt Europium Valence Change in Eu2Pt6Al15 around 45 K

Eu2Pt6Al15 has been prepared from the elements via arc-melting and subsequent temperature treatment; the structure was refined from single crystal X-ray diffraction data. The compound crystallizes in an orthorhombic (3 + 1)­D commensurately modulated structure (Sc2Pt6Al15 type) with space group Cmcm(α,0,0)­0s0 (α = 2/3). Full ordering of the Pt and Al atoms within the [Pt6Al15]δ− polyanion was observed. Magnetic measurements revealed an anomaly in the susceptibility data at T = 41.6(1) K, which was also observed as λ-type anomaly in heat capacity measurements (T = 40.7(1) K). Temperature dependent powder X-ray diffraction experiments indicated a drastic shortening of the c axis (−18 pm, −1.1%) around 45 K, while the a axis nearly remains the same (−1 pm, −0.2%). Measurements of the electrical resistivity verified the anomaly, indicating a clear change in the electronic structure of the material. The observed anomalies in the physical measurements can be explained by a temperature driven first order valence change from Eu2+ at higher temperatures (>55 K) to Eu3+ at low temperatures. This valence change was proven by temperature dependent 151Eu Mössbauer spectroscopic investigations. Isostructural Eu2Pt6Ga15 was prepared in comparison, and it shows divalent Eu atoms down to 2.5 K along with antiferromagnetic ordering at T N = 13.1(1) K.