Bismuth as a Reactive Solvent in the Synthesis of Multicomponent Transition-Metal-Bearing Bismuthides

Abstract

Employment of liquid bismuth (Bi) allows the facile single-crystal growth of compounds containing elements with high melting points, provided that these elements have reasonably high solubility in Bi. Utilization of the Bi flux approach yielded two new ternary bismuthides, SrNi0.17(1)Bi2 [a defect variant of the BaCuSn2 type, space group Cmcm, a = 4.879(2) Å, b = 17.580(6) Å, and c = 4.696(2) Å] and CaTi3Bi4 [NdTi3(Sn0.1Sb0.9)4 structure type, space group Fmmm, a = 5.6295(7) Å, b = 9.8389(1) Å, and c = 23.905(3) Å]. In addition, the ternary antimonide CaV3Sb4, isostructural with CaTi3Bi4, was synthesized from antimony (Sb) flux, and analyzed with the goal of validating structural assessment of the bismuthide analogue, where the X-ray crystallographic work proved to be very challenging. All synthesized compounds exhibit complex crystal structures featuring quasi-two-dimensional building blocks of different topologies. First-principle calculations reveal hypervalent bonding in the homoatomic Bi subunits. Physical property measurements indicate metallic conductivity and the absence of localized magnetism in the studied compounds.

Ultralow Thermal Conductivity and High Thermopower in a New Family of Zintl Antimonides Ca10MSb9 (M = Ga, In, Mn, Zn) with Complex Structures and Heavy Disorder

“…Nevertheless, by careful optimization of the experimental conditions, the Sb flux technique can yield high-quality single crystals, suitable for various characterization techniques. Some recent examples of intermetallic materials obtained in the form of single crystals from liquid Sb (or Sb-rich eutectic mixtures) include the kagome metals CaV 3 Sb 4 70 and AV 3 Sb 5 (A = K, Rb, Cs), 71 the noble metal antimonide La 6 Pd 2+x Sb 15 with a multiband electronic behavior, 72 and Mg 3 Sb 2 with promising thermoelectric performance. 73,74 Our initial exploratory studies in the Ca−M−Sb systems (M = Ga, In), employing the Sb flux technique, were aimed at the synthesis of Ca 11 Sb 10 derivatives with a doping of the M metal in the Sb sites, by analogy with Ca 11 In 2 Bi 8 , which was predicted by us to be a potentially interesting system for testing of thermoelectric performance.…”

Studied and Forgotten. A Fresh Look at the Li–Mn–Ge System

“…Such behavior is not surprising, taking into account the presumed layered crystal structure. Other intermetallic compounds with low‐dimensional, weakly interacting structural units have been often reported to be soft and easily exfoliable …”

“…Other intermetallic compounds with low-dimensional, weakly interacting structural units have been often reported to be soft and easily exfoliable. [18][19][20] Single-crystal X-ray diffraction images from a crystal with good-enough quality were initially indexed in a tetragonal unit cell with a = 4.305(2) Å and c = 6.323(4) Å (at T = 200 K) by including only the most intense reflections [I Ͼ 20σ(I)]. Structure solution was straightforward in space group P4/nmm and confirmed the assignment of the structure to the ZrCuSiAs type.…”

Exploration of Multi-Component Vanadium and Titanium Pnictides Using Flux Growth and Conventional High-Temperature Methods

“…To date, flux growth experiments in the Sr-V-Sb system have resulted in binary antimonides only. In the Ca-V-Sb system, the exploratory work so far has resulted in the phase CaV 3 Sb 4 (Ovchinnikov and Bobev, 2020), which is structurally unrelated to Ba 5 V 12 Sb 19+x .…”