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

doi:10.1016/S0925-8388(97)00038-8

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

Northwestern University

Research output: Contribution to journal › Article

41 Citations (Scopus)

Abstract

Na₈Pb₂(Ge₂S₆)₂, Na₈Sn₂(Ge₂S₆)₂, and Na₈Pb₂(Si₂Se₆)₂ were synthesized by reacting Pb or Sn, Ge, and Na₂S_x or Na₂Se_x 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. D_cale = 3.543 g cm^-3, number of unique data with F²_o>3 σ(F²_o), 645, number of variables, 37. The final R/R_w=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. D_cale= 3.054 g cm^-3, number of unique data with F²_o>3 σ(F²_o), 480, number of variables, 38. The final R/R_w = 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. D_cale=4.190 g cm^-3, number of unique data with F²_o3 >3 σ(F²_o), 494, number of variables, 37. The final R/R_w = 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 language	English
Pages (from-to)	122-128
Number of pages	7
Journal	Journal of Alloys and Compounds
Volume	259
Issue number	1-2
DOIs	https://doi.org/10.1016/S0925-8388(97)00038-8
Publication status	Published - Aug 22 1997

Keywords

Ligand binding
[GeS] ligands
[SiSe] ligands

ASJC Scopus subject areas

Mechanics of Materials
Mechanical Engineering
Metals and Alloys
Materials Chemistry

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10.1016/S0925-8388(97)00038-8

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Marking, G. A., & Kanatzidis, M. G. (1997). 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. Journal of Alloys and Compounds, 259(1-2), 122-128. https://doi.org/10.1016/S0925-8388(97)00038-8

@article{0713c3905a8d42ee8352fbcf7f0854b4,

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.",

keywords = "Ligand binding, [GeS] ligands, [SiSe] ligands",

author = "Marking, {Gregory A.} and Kanatzidis, {Mercouri G.}",

year = "1997",

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doi = "10.1016/S0925-8388(97)00038-8",

language = "English",

volume = "259",

pages = "122--128",

journal = "Journal of Alloys and Compounds",

issn = "0925-8388",

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TY - JOUR

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

Y1 - 1997/8/22

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 - Ligand binding

KW - [GeS] ligands

KW - [SiSe] ligands

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