Non-stoichimometric square sheets in RSe2−<i>x</i> (<i>x</i> ∼ 1/6) (R = Gd and Tb)

The application of optimal electron count has proven effective in predicting the existence of complex structural topologies containing electron-rich polyanionic networks, including linear and zig-zag chains, square planar structures, and simple cubic lattices of main group elements. In this study, we report the successful synthesis of a new family of magnetic compounds, RSe2−x (x ∼ 1/6) (R = Gd and Tb), using KCl flux. The resulting crystal structure of RSe2−x is tetragonal, exhibiting PbFCl-type symmetry with space group P4/nmm. Chemical composition analysis consistently reveals x ∼ 1/6, indicating chalcogen-deficient square sheets. This observation suggests that RSe2−x adheres to the 14-electron rule, as the total valence electrons per RSe2−x (x ∼ 1/6) is 14 e−. In GdSe2−x (x ∼ 1/6), the magnetic susceptibility measurement displays a lambda-shaped peak around 8 K, indicating an antiferromagnetic-type transition. However, the positive Curie–Weiss temperature (θCW) suggests the presence of an additional ferromagnetic interaction, which may result from the large magnetic moment of the Gd atoms. In contrast, TbSe2−x (x ∼ 1/6) exhibits antiferromagnetic ordering. Chemical bonding analysis also indicates that the strong Se–Se antibonding in the square net may be related to Se deficiency. Our work shed light on ellucidating the interplay between chemical rule, defects, and magnetism.