DOE OSTI2024
We outline how pairs of strongly immiscible elements, referred to here as antagonistic pairs, can be used to synthesize ternary compounds with low or quasi-reduced-dimensional motifs intrinsically built into their crystal structures. By identifying third elements that are mutually compatible with a given antagonistic pair, ternary compounds can be formed in which the third element segregates the immiscible atoms into spatially separated substructures. Quasi-low-dimensional structural units, such as sheets, chains, or clusters are a natural consequence of the immiscible atoms seeking to avoid close contact in the solid state. Further, as proof of principle, we present the discovery, crystal growth, and basic physical properties of La 4 Co 4 $\mathrm{X}$ (X = Pb, Bi, Sb), a family of intermetallic compounds based on the antagonistic pairs Co-Pb and Co-Bi. La 4 Co 4 $\mathrm{X}$ adopts an orthorhombic crystal structure (space group Pbam) containing quasi-two-dimensional Co slabs and La-X polyhedra that stack in an alternating manner along the α axis. Consistent with our proposal, the La atoms separate the Co and X substructures, ensuring there are no direct contacts between the members of the immiscible (antagonistic) pair. Within the Co slabs, the atoms occupy the vertices of corner sharing tetrahedra and triangles, and this bonding motif produces narrow electronic bands near the Fermi level that favor magnetism. The Co is moment bearing in each La 4 Co 4 $\mathrm{X}$ compound studied, and we show that whereas La 4 Co 4 Pb behaves as a three-dimensional antiferromagnet with T N =220K, La 4 Co 4 Bi and La 4 Co 4 Sb have behavior consistent with low-dimensional magnetic coupling and ordering, with T N =153K and 143 K, respectively. In addition to the Pb-, Bi-, and Sb-based La 4 Co 4 $\mathrm{X}$ compounds, we also were likely able to produce an analogous La 4 Co 4 Sn in polycrystalline form, although we were unable to isolate single crystals. We anticipate that identifying and using mutually compatible third elements together with an antagonistic pair represents a generalizable design principle for discovering new materials and new structure types containing low-dimensional substructures.