Crystal Structures, Raman Spectroscopy, and Magnetic Properties of Ba_7.5Al₁₃Si₂₉ and Eu_0.27Ba_7.22Al₁₃Si₂₉

The framework-deficient clathrate phases Ba7.5Al13Si29 and Eu0.27Ba7.22Al13Si29 were prepared using a molten Al flux. Single-crystal X-ray diffraction confirmed the two phases to be clathrate type I (space group Pm3̄n). For Eu0.27Ba7.22Al13Si29, single-crystal X-ray diffraction revealed the Eu to partially occupy the 2a position. Microprobe analysis of single crystals provided the stoichiometry, and Raman spectroscopy was used to investigate the guest framework interactions. The Raman spectra are consistent with both Ba7.5Al13Si29 and Eu0.27Ba7.22Al13Si29 having minimal guest−host interactions. Magnetic susceptibility data for Eu0.27Ba7.22Al13Si29 imply weak magnetic ordering and indicate a 2+ oxidation state for the Eu ion.采用熔融铝助熔剂法制备了骨架缺陷型笼形物相Ba7.5Al13Si29与Eu0.27Ba7.22Al13Si29。通过单晶X射线衍射确认，两种物相均为I型笼形化合物，空间群为Pm-3n。针对Eu0.27Ba7.22Al13Si29的单晶X射线衍射分析显示，铕（Eu）离子部分占据2a晶位。通过单晶微探针分析确定了其化学计量比，并采用拉曼光谱探究客体-骨架相互作用。拉曼光谱结果表明，Ba7.5Al13Si29与Eu0.27Ba7.22Al13Si29均存在极弱的客体-主体相互作用。针对Eu0.27Ba7.22Al13Si29的磁化率数据显示其存在弱磁有序现象，同时证明铕离子的氧化态为+2价。