In situ intercalative polymerization chemistry of FeOCl. Generation and properties of novel, highly conductive inorganic/organic polymer microlaminates

Mercouri G Kanatzidis, Henry O. Marcy, William J. McCarthy, Carl R. Kannewurf, Tobin J Marks

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Abstract

New structural forms of polypyrrole and polythiophene are prepared by a chemical method in which intercalation and simultaneous polymerization of pyrrole and 2,2'-bithiophene are brought about within the constrained van der Waals gap of a layered inorganic solid, FeOCl. The reaction of FeOCl with pyrrole and 2,2'-bithiophene yields compounds (C4H3N)0.34FeOCl, I and (C4H2S)0.28FeOCl, II, respectively. (C4H3N)0.34FeOCl and (C4H2S)0.28FeOCl are brown-black microcrystalline solids with a shiny metallic luster. The interlayer spacing in I and II (b-axis) is 13.21(1) Å and 13.31(1) Å, respectively, compared to 7.98(2) Å in pristine FeOCl. X-ray powder diffraction data for I and II are consistent with a space group change from Pmnm (in FeOCl) to Immm or I222 and doubling of the b-axis. The body-centered unit cell results from a lateral shift of the alternate FeOCl layers in the a direction of the ac plane so that the chlorine atoms lie directly on top of each other. The nature of the organic material in I and II was probed by chemical, physical and charge transport techniques, all of which indicate the presence of a high molecular weight, conductive polymer. I and II exhibit high electrical conductivities compared to other FeOCl intercalation compounds. Four-probe electrical conductivity data (in the range 4-300 K) measured on compressed pellets of the materials show thermally activated behavior with room temperature σ≈1ω-1 cm-1. Thermoelectric power measurements indicate predominant hole conduction with metallic behavior. In (C4H2S)0.28FeOCl, as sudden rise in the Seebeck coefficient below ∼ 35 K is observed, suggesting a possible metal-semiconductor transition.

Original languageEnglish
Pages (from-to)594-608
Number of pages15
JournalSolid State Ionics
Volume32-33
Issue numberPART 1
DOIs
Publication statusPublished - 1989

Fingerprint

Inorganic polymers
Pyrroles
Organic polymers
pyrroles
intercalation
polymerization
Polymerization
chemistry
luster
Intercalation compounds
electrical resistivity
Seebeck coefficient
Chlorine
Thermoelectric power
polypyrroles
Polypyrroles
polymers
Polymers
Seebeck effect
Intercalation

ASJC Scopus subject areas

  • Electrochemistry
  • Physical and Theoretical Chemistry
  • Energy Engineering and Power Technology
  • Materials Chemistry
  • Condensed Matter Physics

Cite this

In situ intercalative polymerization chemistry of FeOCl. Generation and properties of novel, highly conductive inorganic/organic polymer microlaminates. / Kanatzidis, Mercouri G; Marcy, Henry O.; McCarthy, William J.; Kannewurf, Carl R.; Marks, Tobin J.

In: Solid State Ionics, Vol. 32-33, No. PART 1, 1989, p. 594-608.

Research output: Contribution to journalArticle

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abstract = "New structural forms of polypyrrole and polythiophene are prepared by a chemical method in which intercalation and simultaneous polymerization of pyrrole and 2,2'-bithiophene are brought about within the constrained van der Waals gap of a layered inorganic solid, FeOCl. The reaction of FeOCl with pyrrole and 2,2'-bithiophene yields compounds (C4H3N)0.34FeOCl, I and (C4H2S)0.28FeOCl, II, respectively. (C4H3N)0.34FeOCl and (C4H2S)0.28FeOCl are brown-black microcrystalline solids with a shiny metallic luster. The interlayer spacing in I and II (b-axis) is 13.21(1) {\AA} and 13.31(1) {\AA}, respectively, compared to 7.98(2) {\AA} in pristine FeOCl. X-ray powder diffraction data for I and II are consistent with a space group change from Pmnm (in FeOCl) to Immm or I222 and doubling of the b-axis. The body-centered unit cell results from a lateral shift of the alternate FeOCl layers in the a direction of the ac plane so that the chlorine atoms lie directly on top of each other. The nature of the organic material in I and II was probed by chemical, physical and charge transport techniques, all of which indicate the presence of a high molecular weight, conductive polymer. I and II exhibit high electrical conductivities compared to other FeOCl intercalation compounds. Four-probe electrical conductivity data (in the range 4-300 K) measured on compressed pellets of the materials show thermally activated behavior with room temperature σ≈1ω-1 cm-1. Thermoelectric power measurements indicate predominant hole conduction with metallic behavior. In (C4H2S)0.28FeOCl, as sudden rise in the Seebeck coefficient below ∼ 35 K is observed, suggesting a possible metal-semiconductor transition.",
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