Synthesis, Crystal and Electronic Structure of the Titanium Bismuthides Sr₅Ti₁₂Bi_19+x, Ba₅Ti₁₂Bi_19+x, and Sr_5–δEu_δTi₁₂Bi_19+x (x ≈ 0.5–1.0; δ ≈ 2.4, 4.0)

Abstract

Crystals of the new ternary bismuthides AE 5 Ti 12 Bi 19+x (AE = Sr, Ba) and Sr 5-δ Eu δ Ti 12 Bi 19+x (δ ≈ 2.4, 4.0; x ≤ 1.0) were grown using an excess of molten Bi as a flux. The title compounds crystallize in the cubic non-centrosymmetric space group P43m and are structurally related to the antimonides Ba 5 M 12 Sb 19+x (M = Ti, V, Nb). The crystal structure features Ti atoms stuffed in the γ-brass-like sub-lattice made of AE (AE = Sr, Ba, Eu) and Bi atoms. The arrangement of the AE atoms, on its own, represents a framework consisting of interconnected regular tetrahedra and octahedra. Another notable attribute of [a]

Undistorted linear Bi chains with hypervalent bonding in La3TiBi5 from single-crystal X-ray diffraction

“…The anionic substructure is represented by two kinds of one-dimensional building blocks running along the c direction -columns of face-sharing TiBi 6 octahedra and linear Bi chains. The interatomic Ti-Bi distance of 2.9384 (5) Å is close to the value obtained by Murakami et al (2017) from powder X-ray diffraction data and lies within the typical range of Ti-Bi bond lengths (Richter & Jeitschko, 1997;Watanabe & Yamane, 2016;Ovchinnikov & Bobev, 2018b). The TiBi 6 octahedra are slightly compressed along c as indicated by the angle of 92.75 (1) for Bi1 x -Ti-Bi1 and 87.26 1…”

Evolution of Highly Anisotropic Magnetism in the Titanium-Based Kagome Metals LnTi3Bi4 (Ln: La···Gd3+, Eu2+, Yb2+)

“…Unfortunately, the high absorption of Ln and Bi, the large sample sizes, and anisotropic geometries combine to make absorption corrections extremely difficult. Such issues have been noted previously in inorganic bismides, ,,, and the analogous difficulties in solving CaTi 3 Bi 4 were the impetus for the discovery of the more mechanically robust CaV 3 Sb 4 compound . Selection of naturally faceted (uncut) crystals, coupled with face-indexing absorption corrections, allowed us to circumvent most mosaic and deformation issues.…”

“…The potential for magnetism through the choice of the A-site provides a degree of chemical flexibility analogous to the AM 6 X 6 family. Reports of the phases are sporadic, with off-hand reports in exploratory chemistry papers. , Systematic, chemistry-focused studies with detailed magnetic characterization are strikingly absent. Our prior discovery of the VSb-based analogues YbV 3 Sb 4 and EuV 3 Sb 4 represent some of the only explorations into the magnetic and transport properties of the wider family of compounds.…”

“…Our prior discovery of the VSb-based analogues YbV 3 Sb 4 and EuV 3 Sb 4 represent some of the only explorations into the magnetic and transport properties of the wider family of compounds. To date, the AM 3 X 4 family is composed of the compounds LaTi 3 Bi 4 , CeTi 3 Bi 4 , EuTi 3 Bi 4 , SmTi 3 Bi 4 , CaV 3 Sb 4 , CaTi 3 Bi 4 , YbV 3 Sb 4 , and EuV 3 Sb 4 . − …”

Flux Growth, Crystal Structures, and Electronic Properties of the Ternary Intermetallic Compounds Ca3Pd4Bi8 and Ca3Pt4Bi8

“…For the Ca–Bi interactions, as well as for the Ca– M contacts, the underoptimization is related to the availability of bonding states above the Fermi level. Due to the complex combination of bonding and antibonding states, not unusual for Bi-rich compounds, 39 , 44 , 51 , 52 the averaged Bi–Bi interaction is comparably weak, although it is essentially optimized at E F .…”