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

Ovchinnikov, Alexander; Bobev, Svilen

doi:10.1021/acs.inorgchem.9b02881

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

Journal Article · Fri Dec 20 00:00:00 EST 2019 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.9b02881· OSTI ID:1595734

^[1];

^[2]

Univ. of Delaware, Newark, DE (United States); Stockholm Univ. (Sweden)
Univ. of Delaware, Newark, DE (United States)

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, α = 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. Lastly, physical property measurements indicate metallic conductivity and the absence of localized magnetism in the studied compounds.

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Research Organization:: Univ. of Delaware, Newark, DE (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0008885

OSTI ID:: 1595734

Alternate ID(s):: OSTI ID: 1698007

Journal Information:: Inorganic Chemistry, Vol. 59, Issue 6; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 5 works

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