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

Alexander Ovchinnikov; Svilen Bobev

doi:10.1021/acs.inorgchem.9b02881

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

Inorg Chem. 2020 Mar 16;59(6):3459-3470. doi: 10.1021/acs.inorgchem.9b02881. Epub 2019 Dec 20.

Authors

Alexander Ovchinnikov^{1

2}, Svilen Bobev¹

Affiliations

¹ Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware 19716, United States.
² Department of Materials and Environmental Chemistry, Stockholm University, Arrhenius väg 16C, Svante 10691, Sweden.

PMID: 31860285
DOI: 10.1021/acs.inorgchem.9b02881

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, SrNi_0.17(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(Sn_0.1Sb_0.9)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.