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Related Concept Videos

Network Covalent Solids02:18

Network Covalent Solids

Network covalent solids contain a three-dimensional network of covalently bonded atoms as found in the crystal structures of nonmetals like diamond, graphite, silicon, and some covalent compounds, such as silicon dioxide (sand) and silicon carbide (carborundum, the abrasive on sandpaper). Many minerals have networks of covalent bonds.
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Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework
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Semiconducting lead-sulfur-organic network solids.

Dayna L Turner1, Thomas P Vaid, Peter W Stephens

  • 1Department of Chemistry and Center for Materials Innovation, Washington University, St. Louis, Missouri 63130, USA.

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New lead coordination polymers synthesized from benzenethiols and ethylenediamine exhibit diverse structures and properties. The resulting materials range from molecular units to inorganic solid-like bonding, with one compound identified as a semiconductor.

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Area of Science:

  • Coordination Chemistry
  • Materials Science
  • Solid-State Chemistry

Background:

  • Lead compounds and their coordination polymers are of interest due to their diverse structural motifs and potential applications.
  • Benzenethiols serve as versatile ligands for constructing complex metal-organic frameworks.

Purpose of the Study:

  • To synthesize and characterize novel lead coordination polymers using different benzenethiol ligands.
  • To investigate the structural diversity and bonding characteristics of these new materials.
  • To explore the relationship between structure and properties, particularly electrical conductivity.

Main Methods:

  • Reactions of lead(II) acetate with 1,2,4,5-benzenetetrathiol, 1,4-benzenedithiol, and benzenehexathiol in ethylenediamine.
  • Structure determination using synchrotron X-ray powder diffraction and single-crystal X-ray diffraction.
  • Analysis of bonding modes and correlation with optical and electrical properties.

Main Results:

  • Synthesis of three distinct lead coordination polymers: [Pb2(S2C6H2S2)(en)]n (yellow), [Pb3(SC6H4S)3(en)2]n (orange-red), and [Pb3C6S6]n (brown).
  • Structural elucidation revealed "molecular" units in [Pb2(S2C6H2S2)(en)]n and inorganic solid-like bonding in [Pb3C6S6]n.
  • [Pb3C6S6]n was identified as a semiconductor, indicating varied electronic properties.

Conclusions:

  • The choice of benzenethiol ligand significantly influences the structure and bonding of lead coordination polymers.
  • The synthesized materials exhibit a spectrum of bonding types, from discrete molecular assemblies to extended inorganic networks.
  • The semiconductor behavior of [Pb3C6S6]n highlights the potential for tuning electronic properties in these lead-sulfur systems.