The ethane-like [Ge2S6]6- and [Si2Se6]6- ligands bound to main-group metals in Na8Pb2[Ge2S6]2, Na8Sn2[Ge2S6]2, and Na8Pb2[Si2Se6]2

Gregory A. Marking, Mercouri G Kanatzidis

Research output: Contribution to journalArticle

40 Citations (Scopus)

Abstract

Na8Pb2(Ge2S6)2, Na8Sn2(Ge2S6)2, and Na8Pb2(Si2Se6)2 were synthesized by reacting Pb or Sn, Ge, and Na2Sx or Na2Sex flux at 850 °C, 750 °C, and 850 °C respectively. Yellow-orange Na8Pb2(Ge2S6)2 crystallizes in the monoclinic space group C2/m (No. 12) with a=6.839(2) Å, b=11.783(2) Å, c=7.744(2) Å, β= 107.00(2) deg, and V=596.7(4) Å3, Z=1. Dcale = 3.543 g cm-3, number of unique data with F2o>3 σ(F2o), 645, number of variables, 37. The final R/Rw=2.9/3.9. Isostructural ruby-red Na8Sn2(Ge2S6)2 crystallizes in the monoclinic space group C2/m (No. 12) with a=6.849(1) Å, b= 11.777(1) Å, c=7.705(1) Å, β=106.44(1) deg, and V=596.1(3) Å3, Z=1. Dcale= 3.054 g cm-3, number of unique data with F2o>3 σ(F2o), 480, number of variables, 38. The final R/Rw = 2.1/2.7. Isostructural red-orange Na8Pb2(Si2Se6)2 crystallizes in the monoclinic space group C2/m (No. 12) with a=7.070(3) Å, b= 12.214(3) Å, c=7.969(3) Å, β=107.29(3) deg, and V=657.1(4) Å3, Z 1. Dcale=4.190 g cm-3, number of unique data with F2o3 >3 σ(F2o), 494, number of variables, 37. The final R/Rw = 2.4/3.4. The structure of these new materials consists of [Ge2S6]6- or [Si2Se6]6- ethane-like fragments surrounded by metal cationic sites which are occupied either by sodium or by mixtures of sodium and lead or tin. The ordering of Pb on these cationic sites leads to a 2-dimensional "layered" morphology for Na8Pb2(Ge2S6)2 while the ordering of Sn on the cationic sites leads to a 3-dimensional "chunky" morphology for Na8Sn2(Ge2S6)2. The ordering of Pb on the cationic sites in Na8Pb2(Si2Se6)2, is the same as the ordering in Na8Pb2(Ge2S6)2 although the crystal morphology is chunky rather than layered. Raman and vibrational spectroscopic data are consistent with the presence of [Ge2S6]6- fragments in the first two compounds. Single crystal optical spectra indicate that these semiconductors have bandgaps of 2.43 eV for Na8Pb2(Ge2S6)2 and 2.06 eV for Na8Sn2(Ge2S6)2.

Original languageEnglish
Pages (from-to)122-128
Number of pages7
JournalJournal of Alloys and Compounds
Volume259
Issue number1-2
Publication statusPublished - Aug 22 1997

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Ethane
Metals
Ligands
Sodium
Ruby
Tin
Energy gap
Lead
Single crystals
Semiconductor materials
Fluxes
Crystals

Keywords

  • [GeS] ligands
  • [SiSe] ligands
  • Ligand binding

ASJC Scopus subject areas

  • Metals and Alloys

Cite this

The ethane-like [Ge2S6]6- and [Si2Se6]6- ligands bound to main-group metals in Na8Pb2[Ge2S6]2, Na8Sn2[Ge2S6]2, and Na8Pb2[Si2Se6]2. / Marking, Gregory A.; Kanatzidis, Mercouri G.

In: Journal of Alloys and Compounds, Vol. 259, No. 1-2, 22.08.1997, p. 122-128.

Research output: Contribution to journalArticle

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title = "The ethane-like [Ge2S6]6- and [Si2Se6]6- ligands bound to main-group metals in Na8Pb2[Ge2S6]2, Na8Sn2[Ge2S6]2, and Na8Pb2[Si2Se6]2",
abstract = "Na8Pb2(Ge2S6)2, Na8Sn2(Ge2S6)2, and Na8Pb2(Si2Se6)2 were synthesized by reacting Pb or Sn, Ge, and Na2Sx or Na2Sex flux at 850 °C, 750 °C, and 850 °C respectively. Yellow-orange Na8Pb2(Ge2S6)2 crystallizes in the monoclinic space group C2/m (No. 12) with a=6.839(2) {\AA}, b=11.783(2) {\AA}, c=7.744(2) {\AA}, β= 107.00(2) deg, and V=596.7(4) {\AA}3, Z=1. Dcale = 3.543 g cm-3, number of unique data with F2o>3 σ(F2o), 645, number of variables, 37. The final R/Rw=2.9/3.9. Isostructural ruby-red Na8Sn2(Ge2S6)2 crystallizes in the monoclinic space group C2/m (No. 12) with a=6.849(1) {\AA}, b= 11.777(1) {\AA}, c=7.705(1) {\AA}, β=106.44(1) deg, and V=596.1(3) {\AA}3, Z=1. Dcale= 3.054 g cm-3, number of unique data with F2o>3 σ(F2o), 480, number of variables, 38. The final R/Rw = 2.1/2.7. Isostructural red-orange Na8Pb2(Si2Se6)2 crystallizes in the monoclinic space group C2/m (No. 12) with a=7.070(3) {\AA}, b= 12.214(3) {\AA}, c=7.969(3) {\AA}, β=107.29(3) deg, and V=657.1(4) {\AA}3, Z 1. Dcale=4.190 g cm-3, number of unique data with F2o3 >3 σ(F2o), 494, number of variables, 37. The final R/Rw = 2.4/3.4. The structure of these new materials consists of [Ge2S6]6- or [Si2Se6]6- ethane-like fragments surrounded by metal cationic sites which are occupied either by sodium or by mixtures of sodium and lead or tin. The ordering of Pb on these cationic sites leads to a 2-dimensional {"}layered{"} morphology for Na8Pb2(Ge2S6)2 while the ordering of Sn on the cationic sites leads to a 3-dimensional {"}chunky{"} morphology for Na8Sn2(Ge2S6)2. The ordering of Pb on the cationic sites in Na8Pb2(Si2Se6)2, is the same as the ordering in Na8Pb2(Ge2S6)2 although the crystal morphology is chunky rather than layered. Raman and vibrational spectroscopic data are consistent with the presence of [Ge2S6]6- fragments in the first two compounds. Single crystal optical spectra indicate that these semiconductors have bandgaps of 2.43 eV for Na8Pb2(Ge2S6)2 and 2.06 eV for Na8Sn2(Ge2S6)2.",
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T1 - The ethane-like [Ge2S6]6- and [Si2Se6]6- ligands bound to main-group metals in Na8Pb2[Ge2S6]2, Na8Sn2[Ge2S6]2, and Na8Pb2[Si2Se6]2

AU - Marking, Gregory A.

AU - Kanatzidis, Mercouri G

PY - 1997/8/22

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N2 - Na8Pb2(Ge2S6)2, Na8Sn2(Ge2S6)2, and Na8Pb2(Si2Se6)2 were synthesized by reacting Pb or Sn, Ge, and Na2Sx or Na2Sex flux at 850 °C, 750 °C, and 850 °C respectively. Yellow-orange Na8Pb2(Ge2S6)2 crystallizes in the monoclinic space group C2/m (No. 12) with a=6.839(2) Å, b=11.783(2) Å, c=7.744(2) Å, β= 107.00(2) deg, and V=596.7(4) Å3, Z=1. Dcale = 3.543 g cm-3, number of unique data with F2o>3 σ(F2o), 645, number of variables, 37. The final R/Rw=2.9/3.9. Isostructural ruby-red Na8Sn2(Ge2S6)2 crystallizes in the monoclinic space group C2/m (No. 12) with a=6.849(1) Å, b= 11.777(1) Å, c=7.705(1) Å, β=106.44(1) deg, and V=596.1(3) Å3, Z=1. Dcale= 3.054 g cm-3, number of unique data with F2o>3 σ(F2o), 480, number of variables, 38. The final R/Rw = 2.1/2.7. Isostructural red-orange Na8Pb2(Si2Se6)2 crystallizes in the monoclinic space group C2/m (No. 12) with a=7.070(3) Å, b= 12.214(3) Å, c=7.969(3) Å, β=107.29(3) deg, and V=657.1(4) Å3, Z 1. Dcale=4.190 g cm-3, number of unique data with F2o3 >3 σ(F2o), 494, number of variables, 37. The final R/Rw = 2.4/3.4. The structure of these new materials consists of [Ge2S6]6- or [Si2Se6]6- ethane-like fragments surrounded by metal cationic sites which are occupied either by sodium or by mixtures of sodium and lead or tin. The ordering of Pb on these cationic sites leads to a 2-dimensional "layered" morphology for Na8Pb2(Ge2S6)2 while the ordering of Sn on the cationic sites leads to a 3-dimensional "chunky" morphology for Na8Sn2(Ge2S6)2. The ordering of Pb on the cationic sites in Na8Pb2(Si2Se6)2, is the same as the ordering in Na8Pb2(Ge2S6)2 although the crystal morphology is chunky rather than layered. Raman and vibrational spectroscopic data are consistent with the presence of [Ge2S6]6- fragments in the first two compounds. Single crystal optical spectra indicate that these semiconductors have bandgaps of 2.43 eV for Na8Pb2(Ge2S6)2 and 2.06 eV for Na8Sn2(Ge2S6)2.

AB - Na8Pb2(Ge2S6)2, Na8Sn2(Ge2S6)2, and Na8Pb2(Si2Se6)2 were synthesized by reacting Pb or Sn, Ge, and Na2Sx or Na2Sex flux at 850 °C, 750 °C, and 850 °C respectively. Yellow-orange Na8Pb2(Ge2S6)2 crystallizes in the monoclinic space group C2/m (No. 12) with a=6.839(2) Å, b=11.783(2) Å, c=7.744(2) Å, β= 107.00(2) deg, and V=596.7(4) Å3, Z=1. Dcale = 3.543 g cm-3, number of unique data with F2o>3 σ(F2o), 645, number of variables, 37. The final R/Rw=2.9/3.9. Isostructural ruby-red Na8Sn2(Ge2S6)2 crystallizes in the monoclinic space group C2/m (No. 12) with a=6.849(1) Å, b= 11.777(1) Å, c=7.705(1) Å, β=106.44(1) deg, and V=596.1(3) Å3, Z=1. Dcale= 3.054 g cm-3, number of unique data with F2o>3 σ(F2o), 480, number of variables, 38. The final R/Rw = 2.1/2.7. Isostructural red-orange Na8Pb2(Si2Se6)2 crystallizes in the monoclinic space group C2/m (No. 12) with a=7.070(3) Å, b= 12.214(3) Å, c=7.969(3) Å, β=107.29(3) deg, and V=657.1(4) Å3, Z 1. Dcale=4.190 g cm-3, number of unique data with F2o3 >3 σ(F2o), 494, number of variables, 37. The final R/Rw = 2.4/3.4. The structure of these new materials consists of [Ge2S6]6- or [Si2Se6]6- ethane-like fragments surrounded by metal cationic sites which are occupied either by sodium or by mixtures of sodium and lead or tin. The ordering of Pb on these cationic sites leads to a 2-dimensional "layered" morphology for Na8Pb2(Ge2S6)2 while the ordering of Sn on the cationic sites leads to a 3-dimensional "chunky" morphology for Na8Sn2(Ge2S6)2. The ordering of Pb on the cationic sites in Na8Pb2(Si2Se6)2, is the same as the ordering in Na8Pb2(Ge2S6)2 although the crystal morphology is chunky rather than layered. Raman and vibrational spectroscopic data are consistent with the presence of [Ge2S6]6- fragments in the first two compounds. Single crystal optical spectra indicate that these semiconductors have bandgaps of 2.43 eV for Na8Pb2(Ge2S6)2 and 2.06 eV for Na8Sn2(Ge2S6)2.

KW - [GeS] ligands

KW - [SiSe] ligands

KW - Ligand binding

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