Intermetallics of 4:4:1 and 3:3:1 series in La–(Co,Ni)–M (M = Bi, Pb, Te, Sb, Sn and Ga, Al) systems and their properties

Abstract

Two series of isostructural intermetallics have been discovered in our search for new compounds with fused honeycomb motifs, both stable at elevated temperatures (1073 K). They crystallize with orthorhombic unit cells – La4Co4M (M = Sn, Sb, Te, Pb, Bi, SG Pbam, a = 8.247–8.315(2), b = 21.913–22.137(7), c = 4.750–4.664(2) Å, V = 850.5–869.5(4) Å3, Z = 4) and La3Ni3M (M = Al, Ga, SG Cmcm, a = 4.1790–4.2395(1), b = 10.4921–10.6426(6), c = 13.6399–13.7616(8) Å, V = 606.72–612.05(7), Z = 3). The crystal structures represent interesting variations of semiregular tilings of corrugated anionic layers and predominantly cationic zigzag motifs. The La4Co4M compounds reveal a complex type of ordering with a high degree of frustration as could be expected for the Kagomé -related lattices, while magnetic ordering in the La3Ni3M series is less evident. Electronic structure calculations have been performed for multiple compounds within both series revealing metallic character and visible local minima around the Fermi level. The bonding picture is characterized by nearly equal contributions from the anionic and the cationic components.