Reaction of aniline with FeOCl. Formation and ordering of conducting polyaniline in a crystalline layered host

C. G. Wu, D. C. DeGroot, H. O. Marcy, J. L. Schindler, Mercouri G Kanatzidis, T. Bakas, V. Papaefthymiou, W. Hirpo, J. P. Yesinowski, Y. J. Liu, M. G. Kanatzidis

Research output: Contribution to journalArticle

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Abstract

A detailed study of the intercalative polymerization reaction of aniline with FeOCl, an extensive physicochemical and spectroscopic characterization of the products, and their oxidative behavior in air is presented. FeOCl reacts with excess aniline in CH3CN at 25 °C, in air, to form black microcrystalline products containing polyaniline (PANI) of the general formula (PANI)xFeOCl (I). X-ray diffraction from a single crystal of (PANI)xFeOCl shows that the polymer is intercalated in an ordered fashion that is commensurate with the FeOCl lattice. This ordering causes a doubling of the unit cell in the two in-plane directions (a- and c-) forming a 2a × 2c superlattice. The PANI can be extracted from (I) by FeOCl framework dissolution in acid. Molecular weight studies of extracted PANI via gel permeation chromatography (GPC) analysis suggest M̄w ∼ 6100 and M̄n ∼ 3500 versus M̄w ∼ 69 000 and M̄n ∼ 7700 observed for bulk PANI. Chain lengths of PANI in the intralamellar space are shorter than those of bulk PANI but show narrower length distribution. Variable temperature 2H-wide-line NMR of (PANI)xFeOCl shows that the polymer chains are significantly confined with respect to phenyl ring rotation, but the spectra are influenced by the electron paramagnetism of the host. The (PANI)xFeOCl was also characterized by infrared spectroscopy, Mössbauer spectroscopy, electron paramagnetic resonance spectroscopy, thermal gravimetric analysis, magnetic susceptibility measurements, and charge-transport measurements. Mössbauer spectroscopy suggests a mixed-valent FeOCl with a Fe2+/Fe3+ ratio in the material ∼1:9. Aerial oxidation of (PANI)xFeOCl yields an intimate mixture of PANI and β-FeOOH. The PANI after oxidation shows a molecular weight intermediate between that extracted from fresh (PANI)xFeOCl and bulk PANI. The electrical conductivity of single crystals is 1.5 × 10-2 S/cm and features a thermally activated temperature dependence consistent with a semiconductor. Thermoelectric power measurements show a positive Seebeck coefficient (∼10 μV/K) at room temperature which increases steadily with decreasing temperature, reaching the value of 100-400 μV/K at 150 K, consistent with a p-type semiconductor. The charge transport data suggest that in (PANI)xFeOCl the reduced FeOCl framework dominates the electronic conduction.

Original languageEnglish
Pages (from-to)9229-9242
Number of pages14
JournalJournal of the American Chemical Society
Volume117
Issue number36
Publication statusPublished - Sep 13 1995

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Aniline
Polyaniline
Crystalline materials
Spectrum Analysis
Semiconductors
Temperature
aniline
polyaniline
Spectroscopy
Charge transfer
Polymers
Molecular Weight
Molecular weight
Air
Single crystals
Semiconductor materials
Paramagnetism
Oxidation
Electric Conductivity
Seebeck coefficient

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Wu, C. G., DeGroot, D. C., Marcy, H. O., Schindler, J. L., Kanatzidis, M. G., Bakas, T., ... Kanatzidis, M. G. (1995). Reaction of aniline with FeOCl. Formation and ordering of conducting polyaniline in a crystalline layered host. Journal of the American Chemical Society, 117(36), 9229-9242.

Reaction of aniline with FeOCl. Formation and ordering of conducting polyaniline in a crystalline layered host. / Wu, C. G.; DeGroot, D. C.; Marcy, H. O.; Schindler, J. L.; Kanatzidis, Mercouri G; Bakas, T.; Papaefthymiou, V.; Hirpo, W.; Yesinowski, J. P.; Liu, Y. J.; Kanatzidis, M. G.

In: Journal of the American Chemical Society, Vol. 117, No. 36, 13.09.1995, p. 9229-9242.

Research output: Contribution to journalArticle

Wu, CG, DeGroot, DC, Marcy, HO, Schindler, JL, Kanatzidis, MG, Bakas, T, Papaefthymiou, V, Hirpo, W, Yesinowski, JP, Liu, YJ & Kanatzidis, MG 1995, 'Reaction of aniline with FeOCl. Formation and ordering of conducting polyaniline in a crystalline layered host', Journal of the American Chemical Society, vol. 117, no. 36, pp. 9229-9242.
Wu, C. G. ; DeGroot, D. C. ; Marcy, H. O. ; Schindler, J. L. ; Kanatzidis, Mercouri G ; Bakas, T. ; Papaefthymiou, V. ; Hirpo, W. ; Yesinowski, J. P. ; Liu, Y. J. ; Kanatzidis, M. G. / Reaction of aniline with FeOCl. Formation and ordering of conducting polyaniline in a crystalline layered host. In: Journal of the American Chemical Society. 1995 ; Vol. 117, No. 36. pp. 9229-9242.
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AU - DeGroot, D. C.

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AU - Schindler, J. L.

AU - Kanatzidis, Mercouri G

AU - Bakas, T.

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N2 - A detailed study of the intercalative polymerization reaction of aniline with FeOCl, an extensive physicochemical and spectroscopic characterization of the products, and their oxidative behavior in air is presented. FeOCl reacts with excess aniline in CH3CN at 25 °C, in air, to form black microcrystalline products containing polyaniline (PANI) of the general formula (PANI)xFeOCl (I). X-ray diffraction from a single crystal of (PANI)xFeOCl shows that the polymer is intercalated in an ordered fashion that is commensurate with the FeOCl lattice. This ordering causes a doubling of the unit cell in the two in-plane directions (a- and c-) forming a 2a × 2c superlattice. The PANI can be extracted from (I) by FeOCl framework dissolution in acid. Molecular weight studies of extracted PANI via gel permeation chromatography (GPC) analysis suggest M̄w ∼ 6100 and M̄n ∼ 3500 versus M̄w ∼ 69 000 and M̄n ∼ 7700 observed for bulk PANI. Chain lengths of PANI in the intralamellar space are shorter than those of bulk PANI but show narrower length distribution. Variable temperature 2H-wide-line NMR of (PANI)xFeOCl shows that the polymer chains are significantly confined with respect to phenyl ring rotation, but the spectra are influenced by the electron paramagnetism of the host. The (PANI)xFeOCl was also characterized by infrared spectroscopy, Mössbauer spectroscopy, electron paramagnetic resonance spectroscopy, thermal gravimetric analysis, magnetic susceptibility measurements, and charge-transport measurements. Mössbauer spectroscopy suggests a mixed-valent FeOCl with a Fe2+/Fe3+ ratio in the material ∼1:9. Aerial oxidation of (PANI)xFeOCl yields an intimate mixture of PANI and β-FeOOH. The PANI after oxidation shows a molecular weight intermediate between that extracted from fresh (PANI)xFeOCl and bulk PANI. The electrical conductivity of single crystals is 1.5 × 10-2 S/cm and features a thermally activated temperature dependence consistent with a semiconductor. Thermoelectric power measurements show a positive Seebeck coefficient (∼10 μV/K) at room temperature which increases steadily with decreasing temperature, reaching the value of 100-400 μV/K at 150 K, consistent with a p-type semiconductor. The charge transport data suggest that in (PANI)xFeOCl the reduced FeOCl framework dominates the electronic conduction.

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