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

Authors:
ORCiD logo [1]; ORCiD logo [2]
  1. Univ. of Delaware, Newark, DE (United States); Stockholm Univ. (Sweden)
  2. Univ. of Delaware, Newark, DE (United States)
Publication Date:
Research Org.:
Univ. of Delaware, Newark, DE (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1595734
Alternate Identifier(s):
OSTI ID: 1698007
Grant/Contract Number:  
SC0008885
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 59; Journal Issue: 6; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; bismuthides; crystal structure; electronic structure; metal-metal bonding

Citation Formats

Ovchinnikov, Alexander, and Bobev, Svilen. Bismuth as a Reactive Solvent in the Synthesis of Multicomponent Transition-Metal-Bearing Bismuthides. United States: N. p., 2019. Web. https://doi.org/10.1021/acs.inorgchem.9b02881.
Ovchinnikov, Alexander, & Bobev, Svilen. Bismuth as a Reactive Solvent in the Synthesis of Multicomponent Transition-Metal-Bearing Bismuthides. United States. https://doi.org/10.1021/acs.inorgchem.9b02881
Ovchinnikov, Alexander, and Bobev, Svilen. Fri . "Bismuth as a Reactive Solvent in the Synthesis of Multicomponent Transition-Metal-Bearing Bismuthides". United States. https://doi.org/10.1021/acs.inorgchem.9b02881. https://www.osti.gov/servlets/purl/1595734.
@article{osti_1595734,
title = {Bismuth as a Reactive Solvent in the Synthesis of Multicomponent Transition-Metal-Bearing Bismuthides},
author = {Ovchinnikov, Alexander and Bobev, Svilen},
abstractNote = {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, α = 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. Lastly, physical property measurements indicate metallic conductivity and the absence of localized magnetism in the studied compounds.},
doi = {10.1021/acs.inorgchem.9b02881},
journal = {Inorganic Chemistry},
number = 6,
volume = 59,
place = {United States},
year = {2019},
month = {12}
}

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Works referencing / citing this record:

Exploration of Multi-Component Vanadium and Titanium Pnictides Using Flux Growth and Conventional High-Temperature Methods
journal, January 2020