Lattice-matched transition metal disulfide intergrowths

The metallic conductors Ag2Te(MS2)3 (M = V, Nb)

Sandy L. Nguyen, Christos D. Malliakas, Melanie C. Francisco, Mercouri G Kanatzidis

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

We present new chalcogenide compounds, Ag2Te(MS 2)3 (M = V, Nb), built up of alternating planes of [MS2] and [Ag2Te]. The Ag and Te atoms are linearly coordinated by S atoms in the [MS2] layers and held in place by covalent interactions. Structural polymorphism was found by single crystal X-ray diffraction studies, where long-range ordering or disorder of the Ag and Te atoms within the hexagonal planar [Ag2Te] layer yielded two distinct crystal forms. When the Ag and Te atoms are ordered, the two isostructural compounds crystallize in the non-centrosymmetric P6Ì...2m space group, with a = 5.5347(8) Å, c = 8.0248(16) Å, and V = 212.89(6) Å3 for α-Ag2Te(VS2)3 and a = 5.7195(8) Å, c = 8.2230(16) Å, and V = 232.96(6) Å3 for α-Ag2Te(NbS2)3. For the occupationally disordered Ag/Te arrangement, a subcell of the ordered phase that crystallizes in the non-centrosymmetric P6Ì...m2 space group, with a = 3.2956(6) Å (=aa/(3)1/2), c = 8.220(2) Å, and V = 77.31(3) Å3 for β-Ag 2Te(VS2)3, was identified. Furthermore, pair distribution function analysis revealed local distortions in the [Ag 2Te] layer. Band structure calculations at the density functional theory level were carried out to investigate the electronic structure of Ag 2Te(MS2)3. Electronic transport measurements on Ag2Te(MS2)3 show that they exhibit p-type metallic behavior. Thermal analyses and temperature-dependent powder X-ray diffraction studies were focused on the stability and transformation/ decomposition of the Ag2Te(MS2)3 phases. Magnetic susceptibility data are also reported. The new intercalated Ag 2Te(MS2)3 system features a unique hypervalent Te with a three-center, four-electron bonding environment isoelectronic to that found in I3 -.

Original languageEnglish
Pages (from-to)6520-6532
Number of pages13
JournalInorganic Chemistry
Volume52
Issue number11
DOIs
Publication statusPublished - Jun 3 2013

Fingerprint

disulfides
Disulfides
Transition metals
conductors
transition metals
Atoms
atoms
polymorphism
Polymorphism
Magnetic susceptibility
diffraction
Band structure
X ray powder diffraction
Electronic structure
Distribution functions
Density functional theory
x rays
distribution functions
Single crystals
disorders

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

Lattice-matched transition metal disulfide intergrowths : The metallic conductors Ag2Te(MS2)3 (M = V, Nb). / Nguyen, Sandy L.; Malliakas, Christos D.; Francisco, Melanie C.; Kanatzidis, Mercouri G.

In: Inorganic Chemistry, Vol. 52, No. 11, 03.06.2013, p. 6520-6532.

Research output: Contribution to journalArticle

Nguyen, Sandy L. ; Malliakas, Christos D. ; Francisco, Melanie C. ; Kanatzidis, Mercouri G. / Lattice-matched transition metal disulfide intergrowths : The metallic conductors Ag2Te(MS2)3 (M = V, Nb). In: Inorganic Chemistry. 2013 ; Vol. 52, No. 11. pp. 6520-6532.
@article{5be7cbcf4e904b989d677c7c43f71930,
title = "Lattice-matched transition metal disulfide intergrowths: The metallic conductors Ag2Te(MS2)3 (M = V, Nb)",
abstract = "We present new chalcogenide compounds, Ag2Te(MS 2)3 (M = V, Nb), built up of alternating planes of [MS2] and [Ag2Te]. The Ag and Te atoms are linearly coordinated by S atoms in the [MS2] layers and held in place by covalent interactions. Structural polymorphism was found by single crystal X-ray diffraction studies, where long-range ordering or disorder of the Ag and Te atoms within the hexagonal planar [Ag2Te] layer yielded two distinct crystal forms. When the Ag and Te atoms are ordered, the two isostructural compounds crystallize in the non-centrosymmetric P6{\`I}...2m space group, with a = 5.5347(8) {\AA}, c = 8.0248(16) {\AA}, and V = 212.89(6) {\AA}3 for α-Ag2Te(VS2)3 and a = 5.7195(8) {\AA}, c = 8.2230(16) {\AA}, and V = 232.96(6) {\AA}3 for α-Ag2Te(NbS2)3. For the occupationally disordered Ag/Te arrangement, a subcell of the ordered phase that crystallizes in the non-centrosymmetric P6{\`I}...m2 space group, with a = 3.2956(6) {\AA} (=aa/(3)1/2), c = 8.220(2) {\AA}, and V = 77.31(3) {\AA}3 for β-Ag 2Te(VS2)3, was identified. Furthermore, pair distribution function analysis revealed local distortions in the [Ag 2Te] layer. Band structure calculations at the density functional theory level were carried out to investigate the electronic structure of Ag 2Te(MS2)3. Electronic transport measurements on Ag2Te(MS2)3 show that they exhibit p-type metallic behavior. Thermal analyses and temperature-dependent powder X-ray diffraction studies were focused on the stability and transformation/ decomposition of the Ag2Te(MS2)3 phases. Magnetic susceptibility data are also reported. The new intercalated Ag 2Te(MS2)3 system features a unique hypervalent Te with a three-center, four-electron bonding environment isoelectronic to that found in I3 -.",
author = "Nguyen, {Sandy L.} and Malliakas, {Christos D.} and Francisco, {Melanie C.} and Kanatzidis, {Mercouri G}",
year = "2013",
month = "6",
day = "3",
doi = "10.1021/ic400483d",
language = "English",
volume = "52",
pages = "6520--6532",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "11",

}

TY - JOUR

T1 - Lattice-matched transition metal disulfide intergrowths

T2 - The metallic conductors Ag2Te(MS2)3 (M = V, Nb)

AU - Nguyen, Sandy L.

AU - Malliakas, Christos D.

AU - Francisco, Melanie C.

AU - Kanatzidis, Mercouri G

PY - 2013/6/3

Y1 - 2013/6/3

N2 - We present new chalcogenide compounds, Ag2Te(MS 2)3 (M = V, Nb), built up of alternating planes of [MS2] and [Ag2Te]. The Ag and Te atoms are linearly coordinated by S atoms in the [MS2] layers and held in place by covalent interactions. Structural polymorphism was found by single crystal X-ray diffraction studies, where long-range ordering or disorder of the Ag and Te atoms within the hexagonal planar [Ag2Te] layer yielded two distinct crystal forms. When the Ag and Te atoms are ordered, the two isostructural compounds crystallize in the non-centrosymmetric P6Ì...2m space group, with a = 5.5347(8) Å, c = 8.0248(16) Å, and V = 212.89(6) Å3 for α-Ag2Te(VS2)3 and a = 5.7195(8) Å, c = 8.2230(16) Å, and V = 232.96(6) Å3 for α-Ag2Te(NbS2)3. For the occupationally disordered Ag/Te arrangement, a subcell of the ordered phase that crystallizes in the non-centrosymmetric P6Ì...m2 space group, with a = 3.2956(6) Å (=aa/(3)1/2), c = 8.220(2) Å, and V = 77.31(3) Å3 for β-Ag 2Te(VS2)3, was identified. Furthermore, pair distribution function analysis revealed local distortions in the [Ag 2Te] layer. Band structure calculations at the density functional theory level were carried out to investigate the electronic structure of Ag 2Te(MS2)3. Electronic transport measurements on Ag2Te(MS2)3 show that they exhibit p-type metallic behavior. Thermal analyses and temperature-dependent powder X-ray diffraction studies were focused on the stability and transformation/ decomposition of the Ag2Te(MS2)3 phases. Magnetic susceptibility data are also reported. The new intercalated Ag 2Te(MS2)3 system features a unique hypervalent Te with a three-center, four-electron bonding environment isoelectronic to that found in I3 -.

AB - We present new chalcogenide compounds, Ag2Te(MS 2)3 (M = V, Nb), built up of alternating planes of [MS2] and [Ag2Te]. The Ag and Te atoms are linearly coordinated by S atoms in the [MS2] layers and held in place by covalent interactions. Structural polymorphism was found by single crystal X-ray diffraction studies, where long-range ordering or disorder of the Ag and Te atoms within the hexagonal planar [Ag2Te] layer yielded two distinct crystal forms. When the Ag and Te atoms are ordered, the two isostructural compounds crystallize in the non-centrosymmetric P6Ì...2m space group, with a = 5.5347(8) Å, c = 8.0248(16) Å, and V = 212.89(6) Å3 for α-Ag2Te(VS2)3 and a = 5.7195(8) Å, c = 8.2230(16) Å, and V = 232.96(6) Å3 for α-Ag2Te(NbS2)3. For the occupationally disordered Ag/Te arrangement, a subcell of the ordered phase that crystallizes in the non-centrosymmetric P6Ì...m2 space group, with a = 3.2956(6) Å (=aa/(3)1/2), c = 8.220(2) Å, and V = 77.31(3) Å3 for β-Ag 2Te(VS2)3, was identified. Furthermore, pair distribution function analysis revealed local distortions in the [Ag 2Te] layer. Band structure calculations at the density functional theory level were carried out to investigate the electronic structure of Ag 2Te(MS2)3. Electronic transport measurements on Ag2Te(MS2)3 show that they exhibit p-type metallic behavior. Thermal analyses and temperature-dependent powder X-ray diffraction studies were focused on the stability and transformation/ decomposition of the Ag2Te(MS2)3 phases. Magnetic susceptibility data are also reported. The new intercalated Ag 2Te(MS2)3 system features a unique hypervalent Te with a three-center, four-electron bonding environment isoelectronic to that found in I3 -.

UR - http://www.scopus.com/inward/record.url?scp=84878634228&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84878634228&partnerID=8YFLogxK

U2 - 10.1021/ic400483d

DO - 10.1021/ic400483d

M3 - Article

VL - 52

SP - 6520

EP - 6532

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 11

ER -