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Title: Synthesis, Structure, and Bonding of Eu3Bi(Sn,Bi)4. A Rare Inverse-Cr5B3-Type Structure with a New Tin/Bismuth Network

Abstract

No abstract prepared.

Authors:
;
Publication Date:
Research Org.:
Ames Laboratory (AMES), Ames, IA
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
912762
Report Number(s):
IS-J 7219
Journal ID: ISSN 0020-1669; INOCAJ; TRN: US200801%%1183
DOE Contract Number:
DE-AC02-07CH11358
Resource Type:
Journal Article
Resource Relation:
Journal Name: Inorganic Chemistry; Journal Volume: 46; Journal Issue: 17
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; BONDING; SYNTHESIS; CHEMISTRY; TIN; BISMUTH

Citation Formats

Ming-Hui Ge, and John D. Corbett. Synthesis, Structure, and Bonding of Eu3Bi(Sn,Bi)4. A Rare Inverse-Cr5B3-Type Structure with a New Tin/Bismuth Network. United States: N. p., 2007. Web. doi:10.1021/ic070281c.
Ming-Hui Ge, & John D. Corbett. Synthesis, Structure, and Bonding of Eu3Bi(Sn,Bi)4. A Rare Inverse-Cr5B3-Type Structure with a New Tin/Bismuth Network. United States. doi:10.1021/ic070281c.
Ming-Hui Ge, and John D. Corbett. Mon . "Synthesis, Structure, and Bonding of Eu3Bi(Sn,Bi)4. A Rare Inverse-Cr5B3-Type Structure with a New Tin/Bismuth Network". United States. doi:10.1021/ic070281c.
@article{osti_912762,
title = {Synthesis, Structure, and Bonding of Eu3Bi(Sn,Bi)4. A Rare Inverse-Cr5B3-Type Structure with a New Tin/Bismuth Network},
author = {Ming-Hui Ge and John D. Corbett},
abstractNote = {No abstract prepared.},
doi = {10.1021/ic070281c},
journal = {Inorganic Chemistry},
number = 17,
volume = 46,
place = {United States},
year = {Mon Feb 12 00:00:00 EST 2007},
month = {Mon Feb 12 00:00:00 EST 2007}
}
  • Two new ternary bismuth chalcogenides, Bi{sub 3}In{sub 4}S{sub 10} and Bi{sub 14.7}In{sub 11.3}S{sub 38}, were synthesized from the reactions of binary sulfides via a two-step flux technique. Single-crystal X-ray diffraction analyses indicate that Bi{sub 3}In{sub 4}S{sub 10} crystallizes in the non-centrosymmetric space group Pm and Bi{sub 14.7}In{sub 11.3}S{sub 38} crystallizes in the centrosymmetric space group P2{sub 1}/m. Both compounds adopt three-dimensional frameworks. A distinct structural feature in the two structures is the presence of chains of Bi atoms with alternating short Bi-Bi bonds of around 3.1 A and longer distances of around 4.6 A. The optical band gaps of 1.42(2)more » eV for Bi{sub 3}In{sub 4}S{sub 10} and 1.45(2) eV for Bi{sub 14.7}In{sub 11.3}S{sub 38} were deduced from the diffuse reflectance spectra. - Graphical abstract: Two new bismuth sulfides Bi{sub 3}In{sub 4}S{sub 10} and Bi{sub 14.7}In{sub 11.3}S{sub 38} have been synthesized and characterized. The figure is the arrangement of Bi1 atoms along the b direction with alternating short and long distances (A) in Bi{sub 3}In{sub 4}S{sub 10}. Display Omitted« less
  • Two new bismuth(III) selenite/tellurite nitrates, [(Bi{sub 3}O{sub 2})(SeO{sub 3}){sub 2}](NO{sub 3}) and [Bi(TeO{sub 3})](NO{sub 3}), have been synthesized by conventional facile hydrothermal method at middle temperature 200 °C and characterized by single-crystal X-ray diffraction, powder diffraction, UV–vis–NIR optical absorption spectrum, infrared spectrum and thermal analylsis. Both [(Bi{sub 3}O{sub 2})(SeO{sub 3}){sub 2}](NO{sub 3}) and [Bi(TeO3)](NO3) crystallize in the monoclinic centronsymmetric space group P2{sub 1}/c with a=9.9403(4) Å, b=9.6857(4) Å, c=10.6864(5) Å, β=93.1150(10)° for [(Bi{sub 3}O{sub 2})(SeO{sub 3}){sub 2}](NO{sub 3}) and a=8.1489(3) Å, b=9.0663(4) Å, c=7.4729(3) Å, β=114.899(2)° for Bi(TeO3)(NO3), respectively. The two compounds, whose structures are composed of three different asymmetricmore » building units, exhibit two different types of structures. The structure of [(Bi{sub 3}O{sub 2})(SeO{sub 3}){sub 2}](NO{sub 3}) features a three-dimensional (3D) bismuth(III) selenite cationic tunnel structure [(Bi{sub 3}O{sub 2})(SeO{sub 3}){sub 2}] {sup 3}{sub ∞} with NO{sub 3}{sup −} anion group filling in the 1D tunnel along b axis. The structure of [Bi(TeO{sub 3})](NO{sub 3}) features 2D bismuth(III) tellurite [Bi(TeO{sub 3}){sub 2}]{sup 2}{sub ∞} layers separated by NO{sub 3}{sup −} anion groups. The results of optical diffuse-reflectance spectrum measurements and electronic structure calculations based on density functional theory methods show that the two compounds are wide band-gap semiconductors. - Graphical abstract: Two novel bismuth{sup III} selenite/tellurite nitrates [(Bi{sub 3}O{sub 2})(SeO{sub 3}){sub 2}](NO{sub 3}) with 3D tunnel structure and [Bi(TeO{sub 3})](NO{sub 3}) with 2D layer structure have been firstly synthesized and characterized. Display Omitted - Highlights: • Two novel bismuth{sup III} nitrates [(Bi{sub 3}O{sub 2})(SeO{sub 3}){sub 2}](NO{sub 3}) and [Bi(TeO{sub 3})](NO{sub 3}) were firstly synthesized. • The two compounds were wide band-gap semiconductors.« less
  • Single-crystals of the novel rare-earth metal-bismuth digermanides with idealized formula RE[Bi{sub x}Ge{sub 1-x}]{sub 2} (RE=Y, Pr, Nd, Sm, Gd-Tm, Lu; x<0.16(1)) have been obtained using the Bi-flux technique. Their structures have been established by single-crystal X-ray diffraction; they can be divided into three classes, closely related to the ZrSi{sub 2} structure with the space group Cmcm (no. 63). The structural relationship and the variations with the type of the rare-earth metal have been explored and discussed. Temperature-dependent magnetization measurements on the single-crystals reveal magnetic behavior, which have been rationalized based on the mean-field theory. At cryogenic temperatures, the localized 4fmore » electrons in most of the compounds exhibit antiferromagnetic ordering, mediated by the conduction electrons via Ruderman-Kittel-Kasuya-Yosida (RKKY) exchange interactions. - Graphical abstract: This paper details the synthesis and the structural characterization of an extended series of rare-earth metal-bismuth-germanides RE[Bi{sub x}Ge{sub 1-x}]{sub 2} (RE=Y, Pr-Sm, Gd-Tm, Lu). They crystallize with the same extended symmetry (space group Cmcm), but with three distinct structures, which are closely related. Magnetization measurements show low-temperature antiferromagnetic ordering. RE[Bi{sub x}Ge{sub 1-x}]{sub 2} are the first compounds between these elements. Highlights: Black-Right-Pointing-Pointer RE[Bi{sub x}Ge{sub 1-x}]{sub 2} (RE=rare-earth metal) are the first compounds of the respective elements. Black-Right-Pointing-Pointer Their structures are closely related. Black-Right-Pointing-Pointer Three structures can be distinguished based on the packing of the REGe{sub 6} triangular prisms. Black-Right-Pointing-Pointer All compounds show low-temperature antiferromagnetic ordering.« less
  • The two hitherto unknown compounds Bi{sub 14}P{sub 4}O{sub 31} and Bi{sub 50}V{sub 4}O{sub 85} were prepared by the direct solid-state reaction of Bi{sub 2}O{sub 3} and (NH{sub 4})H{sub 2}PO{sub 4} or V{sub 2}O{sub 5}, respectively. Bi{sub 14}P{sub 4}O{sub 31} crystallizes in a C-centred monoclinic symmetry (C2/c space group) with the unit-cell parameters: a=19.2745(2)A, b=11.3698(1)A, c=52.4082(2)A and {beta}=93.63(1){sup o} (Z=16). The symmetry of Bi{sub 50}V{sub 4}O{sub 85} is also monoclinic (I2/m space group) with lattice parameters of a=11.8123(3)A, b=11.7425(2)A, c=16.5396(2)A and {beta}=90.14(1){sup o} (Z=2). Both structures correspond to a fluorite-type superstructure where the Bi and P or V atoms are orderedmore » in the framework. An idealized structural model is proposed where the structures result of the stacking of mixed atomic layers of composition [Bi{sub 14}M{sub 4}O{sub 31}] and [Bi{sub 18}O{sub 27}] respectively. This new family can be formulated Bi{sub 18-4m}M{sub 4m}O{sub 27+4m} with M=P, V and where the parameter m (0=<m=<1) represents the ratio of the number of [Bi{sub 14}M{sub 4}O{sub 31}] layers to the total number of layers in the sequence. Bi{sub 14}P{sub 4}O{sub 31} corresponds to m=1 when Bi{sub 50}V{sub 8}O{sub 85} corresponds to m=1/3. In this last case, the structural sequence is simply one [Bi{sub 14}V{sub 4}O{sub 31}] layer to two [Bi{sub 18}O{sub 27}] layers. As predicted by the proposed structural building principle, Bi{sub 14}P{sub 4}O{sub 31} is not a good ionic conductor. The conductivity at 650 deg. C is 4 orders of magnitude lower from those found in Bi{sub 46}M{sub 8}O{sub 89} (M=P, V) (m=2/3) and Bi{sub 50}V{sub 4}O{sub 85} (m=1/3)« less