Synthesis and electrochemical properties of mixed ionic and electronic modified polycarbazole

doi:10.1016/S0013-4686(02)00171-8

Electrochimica Acta

Volume 47, Issue 18, 18 July 2002, Pages 2927-2936

https://doi.org/10.1016/S0013-4686(02)00171-8 Get rights and content

Abstract

A carbazole N-substituted by an oxyethylene group was polymerized using oxidative electro-polymerization. Due to the hydrophilic properties of the oligooxyethylene substituent, this monomer can be solubilized and electropolymerized in aqueous electrolyte solution. An acidic medium is particularly appropriate in order to decrease the oxidative potential and to obtain films mainly composed of short oligomers as revealed by GPC analysis. By comparison, the chemical polymerization of the corresponding 3,6 dibromo derivative leads to oligomers with well-defined structure and leads to the obtention of longer macromolecular chains. Electrochromic properties of these materials have been studied and a transition from colorless to deep green has been observed during the oxidation. More particularly interesting are the stability of such materials during polarization and the kinetics of diffusion of the counter ion in the film. In acidic medium 1.25 mol l⁻¹ HClO₄, 95% of the charge density was maintained after polarization for 7000 cycles which shows the good electrochemical stability of this material compared with other polycarbazoles. Diffusion coefficient have been evaluated in aqueous media about D_ClO₄⁻=10⁻¹¹ cm² s⁻¹. Moreover, films are electroactive in oxyethylene based electrolytes. Then, they are probably well-compatible with hydrophilic poly(oxyethylene) solid electrolytes such that all-polymer devices may be prepared.

Introduction

Although less studied than other families of conducting polymers such as polyaniline, polypyrrole, polythiophene or polyparaphenylene, polycarbazoles are of particular interest with regards to their photoconductivity [1], [2], electrochromic properties [3], [4], [5], [6], for their application in electroluminescent devices [7], [8], [9], [10], [11], [12], [13], such as biosensor [14], [15], [16] and others applications[17], [18], [19].

Two main routes are commonly used in order to synthesize poly (N-substituted carbazole)s:

The first one is based on the activation of the carbonhalogen bond of a 3,6-dihalogenated monomer [20] in the presence of a zero valent nickel complex [21], [22], [23]. This dehalogenative polycondensation can be carried out by a chemical [21] or an electrochemical reductive route [22], [23] and leads to well-defined polymers with 3,6 linkages strictly.

The second and probably most commonly used route consists in the electrochemical [24], [25], [26], [27], [28], [29], [30], [31], [32], [33], [34] or chemical [25], [26], [27], [28], [29], [30], [31], [32], [33], [34], [35], [36], [37] oxidation of carbazole derivatives in solution. In their work, Lacaze et al. electropolymerized N-ethyl and N-phenyl carbazole in acetonitrile [26]. The resulting films were composed of short oligomers [27]. Mengoli et al. showed that the electrooxidation of carbazole derivatives in hydroalcoholic acidic medium leads to films with good mechanical and well defined redox properties [28], [29], [30]. Nevertheless, whatever the synthetic pathway, the electrochemical stability of polycarbazole films appears to be limited in comparison with the stability of some other conducting polymer films but it can be significantly improved by decreasing the polydispersity of the material [38].

This work deals with the electrochemical properties of oxyethylene N-substituted polycarbazoles (named PCzOE). Simonet et al. have previously studied the electrosynthesis of different oligoether substituted carbazoles in organic media [31]. These authors have successfully electropolymerized different monomers consisting in short oligoether chains disubstituted by carbazole moieties and observed that the resulting redox polymer was mainly made of dicarbazyl units linked to each other by polyether spacers.

In this work, the electropolymerisation and chemical polymerization of the two monomers 1 and 2 was investigated.

Due to the hydrophilic properties of the oxyethylene substituent, we showed that monomer 1 can be solubilized and electropolymerized in aqueous electrolyte solution. The influence of the medium composition on the electropolymerization conditions and the macromolecular and electrochemical properties of the films is discussed in detail. In order to increase the molecular weight of the polymer and to compare properties of films we have also synthesized oxyethylene substituted polycarbazole by dehalogenative polycondensation of monomer 2. The stability and electrochromic properties of the films depending on the synthesis pathway, are reported. Moreover, the influence of the oxyethylene group on the diffusion coefficient of the counter ions in the film and on its electroactivity in hydrophilic oxyethylene based electrolytes is also presented.

Section snippets

Instrumentation

All electrochemical studies were performed using a PRT-20-2X potentiostat associated with IG6-N integrator (Radiometer). All curves were plotted on an X-Y recorder (DELFT BV BD94 Kipp and Zonen). Electrochemical experiments were run in a conventional three electrode cell. The working electrode was a platinum disc (1 cm diameter) or SnO₂ coated glass (1 cm² area). The counter electrode was a platinum wire. The reference electrode was a saturated calomel electrode (SCE) for all the

Electrochemical polymerization of monomer 1

The electropolymerization of carbazole derivatives in non-organic media has been generally studied in hydroalcoholic mixtures of perchloric acid and methanol which allows to solubilize poorly water soluble monomers [28], [29], [30]. Thanks to the good hydrophilic properties of the oxyethylene chain, the monomer can be solubilized in water and electropolymerized without alcohol.

The curve B of Fig. 1 shows the cyclic voltammograms of a 10⁻³ mol l⁻¹ of monomer 1 in 0.1 mol l⁻¹ LiClO₄/H₂O. On the

Conclusion

We have synthesized two N-oligoether carbazole monomers, which have been, respectively, electropolymerized and polymerized by polycondensation. Hydrophilic oligooxyethylene substituents, allowed solubility and electropolymerization of monomer 1 in aqueous electrolyte. An acidic medium is particularly appropriate to decrease the oxidation potential of the monomer which could lead to the formation of more stable materials. SEC analysis indicates that films are composed of short oligomers. By

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Synthesis and electrochemical properties of mixed ionic and electronic modified polycarbazole

Abstract

Introduction

Section snippets

Instrumentation

Electrochemical polymerization of monomer 1

Conclusion

Eur. Polym. J.

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