来源:ACS Publications
In solid-state compounds, the valence of europium can sometimes be mixed, which is especially favored in structures with several positions for the europium atoms. In this work, we study the Eu-based intermetallic noncentrosymmetric system Eu11–xHg54+x, which has 65 atoms per unit cell and 4 distinct crystallographic positions for europium and 14 positions for mercury. Our detailed analysis of the magnetism of large single crystals suggests that europium in Eu11–xHg54+x might be present in two valence states, resulting in a fragile magnetic ground state. Due to the cage-like structure with a large distance between the Eu atoms, those atoms are weakly ferromagnetically coupled and Eu11–xHg54+x orders at low temperatures, below T1 = 5.5 K, with a subsequent spin reorientation at T2 = 4.3 K. There is no sign of magnetic frustration. Interestingly, the magnetic ordering of the europium substructure results in a magnetization pole reversal with a delicate ferrimagnetic ground state. Additional magnetic phases can be induced by the application of a modest external magnetic field.