Polymerization of 3,4-difluoropyrrole: Electrochemical and physicochemical behavior of poly(difluoropyrrole)

P. Audebert, F. Miomandre, S. G. Di Magno, V. V. Smirnov, P. Hapiot

Research output: Contribution to journalArticle

22 Citations (Scopus)

Abstract

The electrochemical polymerization of 3,4-difluoropyrrole (DFP) has been examined by cyclic voltammetry (CV) as a function of scan rate and solvent. The polymerization is facile in dichloroethane, leading to a stable electroactive film. In contrast, the corresponding polymerization in acetonitrile occurs only with difficulty. Poly(3,4-difluoropyrrole) (PDFP) exhibits a high redox potential (+0.90 V vs Ag/AgCl), a particularly high doping level (ca. 55%), and a rather good conductivity (up to 0.1 S·cm-1), in comparison to other polyhalopyrroles. Meanwhile, the lifetime of the DFP radical cation, as determined by fast scan CV experiments, is about 1 ms. This lifetime is substantially longer than that of other pyrrole derivatives under identical experimental conditions. Theoretical calculations are in agreement with experiment in showing that the DFP radical cation is a powerful oxidant in comparison to pyrrole radical cation. However, these computational studies indicate that the net charge and spin distributions are similar for the cation radicals of DFP and pyrrole itself. To interpret these results, we propose that the introduction of fluorine substituents could be responsible for a lower polarizability of the cation radical, leading to a higher activation barrier for dimerization of DFP in comparison to pyrrole and other halopyrroles.

Original languageEnglish (US)
Pages (from-to)2025-2030
Number of pages6
JournalChemistry of Materials
Volume12
Issue number7
DOIs
StatePublished - Jan 1 2000

Fingerprint

Pyrroles
Cations
Positive ions
Polymerization
Cyclic voltammetry
Ethylene Dichlorides
Electropolymerization
Dimerization
Fluorine
Acetonitrile
Oxidants
Experiments
Chemical activation
Doping (additives)
Derivatives

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)
  • Materials Chemistry

Cite this

Polymerization of 3,4-difluoropyrrole : Electrochemical and physicochemical behavior of poly(difluoropyrrole). / Audebert, P.; Miomandre, F.; Di Magno, S. G.; Smirnov, V. V.; Hapiot, P.

In: Chemistry of Materials, Vol. 12, No. 7, 01.01.2000, p. 2025-2030.

Research output: Contribution to journalArticle

Audebert, P. ; Miomandre, F. ; Di Magno, S. G. ; Smirnov, V. V. ; Hapiot, P. / Polymerization of 3,4-difluoropyrrole : Electrochemical and physicochemical behavior of poly(difluoropyrrole). In: Chemistry of Materials. 2000 ; Vol. 12, No. 7. pp. 2025-2030.
@article{3ce1a10009ff424ab81f3d8b9e316cf3,
title = "Polymerization of 3,4-difluoropyrrole: Electrochemical and physicochemical behavior of poly(difluoropyrrole)",
abstract = "The electrochemical polymerization of 3,4-difluoropyrrole (DFP) has been examined by cyclic voltammetry (CV) as a function of scan rate and solvent. The polymerization is facile in dichloroethane, leading to a stable electroactive film. In contrast, the corresponding polymerization in acetonitrile occurs only with difficulty. Poly(3,4-difluoropyrrole) (PDFP) exhibits a high redox potential (+0.90 V vs Ag/AgCl), a particularly high doping level (ca. 55{\%}), and a rather good conductivity (up to 0.1 S·cm-1), in comparison to other polyhalopyrroles. Meanwhile, the lifetime of the DFP radical cation, as determined by fast scan CV experiments, is about 1 ms. This lifetime is substantially longer than that of other pyrrole derivatives under identical experimental conditions. Theoretical calculations are in agreement with experiment in showing that the DFP radical cation is a powerful oxidant in comparison to pyrrole radical cation. However, these computational studies indicate that the net charge and spin distributions are similar for the cation radicals of DFP and pyrrole itself. To interpret these results, we propose that the introduction of fluorine substituents could be responsible for a lower polarizability of the cation radical, leading to a higher activation barrier for dimerization of DFP in comparison to pyrrole and other halopyrroles.",
author = "P. Audebert and F. Miomandre and {Di Magno}, {S. G.} and Smirnov, {V. V.} and P. Hapiot",
year = "2000",
month = "1",
day = "1",
doi = "10.1021/cm000222w",
language = "English (US)",
volume = "12",
pages = "2025--2030",
journal = "Chemistry of Materials",
issn = "0897-4756",
publisher = "American Chemical Society",
number = "7",

}

TY - JOUR

T1 - Polymerization of 3,4-difluoropyrrole

T2 - Electrochemical and physicochemical behavior of poly(difluoropyrrole)

AU - Audebert, P.

AU - Miomandre, F.

AU - Di Magno, S. G.

AU - Smirnov, V. V.

AU - Hapiot, P.

PY - 2000/1/1

Y1 - 2000/1/1

N2 - The electrochemical polymerization of 3,4-difluoropyrrole (DFP) has been examined by cyclic voltammetry (CV) as a function of scan rate and solvent. The polymerization is facile in dichloroethane, leading to a stable electroactive film. In contrast, the corresponding polymerization in acetonitrile occurs only with difficulty. Poly(3,4-difluoropyrrole) (PDFP) exhibits a high redox potential (+0.90 V vs Ag/AgCl), a particularly high doping level (ca. 55%), and a rather good conductivity (up to 0.1 S·cm-1), in comparison to other polyhalopyrroles. Meanwhile, the lifetime of the DFP radical cation, as determined by fast scan CV experiments, is about 1 ms. This lifetime is substantially longer than that of other pyrrole derivatives under identical experimental conditions. Theoretical calculations are in agreement with experiment in showing that the DFP radical cation is a powerful oxidant in comparison to pyrrole radical cation. However, these computational studies indicate that the net charge and spin distributions are similar for the cation radicals of DFP and pyrrole itself. To interpret these results, we propose that the introduction of fluorine substituents could be responsible for a lower polarizability of the cation radical, leading to a higher activation barrier for dimerization of DFP in comparison to pyrrole and other halopyrroles.

AB - The electrochemical polymerization of 3,4-difluoropyrrole (DFP) has been examined by cyclic voltammetry (CV) as a function of scan rate and solvent. The polymerization is facile in dichloroethane, leading to a stable electroactive film. In contrast, the corresponding polymerization in acetonitrile occurs only with difficulty. Poly(3,4-difluoropyrrole) (PDFP) exhibits a high redox potential (+0.90 V vs Ag/AgCl), a particularly high doping level (ca. 55%), and a rather good conductivity (up to 0.1 S·cm-1), in comparison to other polyhalopyrroles. Meanwhile, the lifetime of the DFP radical cation, as determined by fast scan CV experiments, is about 1 ms. This lifetime is substantially longer than that of other pyrrole derivatives under identical experimental conditions. Theoretical calculations are in agreement with experiment in showing that the DFP radical cation is a powerful oxidant in comparison to pyrrole radical cation. However, these computational studies indicate that the net charge and spin distributions are similar for the cation radicals of DFP and pyrrole itself. To interpret these results, we propose that the introduction of fluorine substituents could be responsible for a lower polarizability of the cation radical, leading to a higher activation barrier for dimerization of DFP in comparison to pyrrole and other halopyrroles.

UR - http://www.scopus.com/inward/record.url?scp=0033798267&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0033798267&partnerID=8YFLogxK

U2 - 10.1021/cm000222w

DO - 10.1021/cm000222w

M3 - Article

AN - SCOPUS:0033798267

VL - 12

SP - 2025

EP - 2030

JO - Chemistry of Materials

JF - Chemistry of Materials

SN - 0897-4756

IS - 7

ER -