The synthesis of novel 3-substituted polypyrroles bearing crown-ether moieties and a study of their electrochemical properties

A series of fourteen novel pyrrole monomers substituted at the 3-position with aliphatic and aromatic crown-ether moieties have been synthesised in good yield and characterised extensively. Several of these compounds were electropolymerised successfully in acetonitrile, using both potentiostatic and galvanostatic modes and the electrochemical properties of those systems were studied via cyclic voltammetry in aqueous and organic media. Novel crown-ether substituted polypyrrole derivatives revealed reversible redox couples in LiClO4/CH3CN (0.1 M). The morphology of these novel crown-ether substituted polypyrrole derivatives was characterised by scanning electron microscopy. These polymers exhibited an open porous structure and half the charge was required when compared to polypyrrole to afford films of equal thickness. The mass change during polymerisation was followed by electrochemical quartz crystal microbalance measurement, and the rate of polymer growth was found to be nonlinear when compared to polypyrrole. (c) 2005 Elsevier B.V. All rights reserved.

The phenomenon of mutual media in polypyrrole with electroactive ions

The dependence of the differential capacitance of polypyrrole doped with several typical dopants on potential is presented, which shows that the differential capacitance varies with the potential, the doped polypyrroles with electroactive ions give the largest capacitance near their formal potentials, which is attributed to the mutual media for electron transfer between polypyrrole and electroactive dopants. The existence of two conducting phases was observed in the complex capacitance plots. The electroactive anions act as an intra-conducting-phase medium for electron transfer, the electroactive cations act as an inter-conducting-phase medium for electron transfer. The mutual media between polypyrrole and redox dopants lead to the increase of the discharging time.

Electropolymeric generation of optically active polypyrrole

The facile synthesis of optically active polypyrrole has been achieved via the enantioselective electropolymerization of pyrrole on indium-tin-oxide-coated glass electrodes in aqueous solution containing D-(+) or L-(-) tartaric acid, (1S)-(+)-10-camphorsulfonic acid and L-lactic acid. The dark films of conducting polypyrroles salt formed under electrostatic conditions (+0.65V vs. Ag/AgCl) exhibited strong circular dichroism (CD) spectra typical of polymers possessing helical chirality. The quantitative reversal of the CD spectrum of the salt grown in (+)-tartaric acid as opposed to (-)-tartaric acid suggests that electropolymerization is highly enantioselective, with one helical screw of the polymer chain being preferentially produced depending on the hand of the tartaric anion incorporated. (C) 1997 Elsevier Science Ltd.

Conducting nanofibres produced by electrospinning

Electrospun fibres based on polypyrrole have been prepared. The incorporation of preformed polypyrrole into fibres electrospun from a carrier polymer can only be achieved when materials are prepared with particulates smaller than the cross-section of the fibre; even so there are some problems, with the substantial loss of material from the electrode tip. As an alternative approach, soluble polypyrroles can be prepared but these are not of sufficient viscosity to prepare electrospun fibres, once again a carrier polymer must be employed. More effective loadings are gained by the process of coating the outer surface of a pre-spun fibre; in this way electrospun fibres coated with polypyrrole can be prepared. This approach has been adapted to produce silver coated polymer fibres by the use of copolymers of styrene and 3-vinyl benzaldehyde.

Generating heat from conducting polypyrrole-coated PET fabrics

Heating effects in polypyrrole-coated polyethyleneterephthalate (PET)-Lycra® fabrics were studied. Chemical synthesis was employed to coat the PET fabrics by polypyrrole using ferric chloride as oxidant and antraquinone- 2-sulfonic acid (AQSA) and naphthalene sulfonic acid (NSA) as dopants. The coated fabrics exhibited reasonable electrical stability, possessed high electrical conductivity, and were effective in heat generation. Surface resistance of polypyrrole-coated fabrics ranged from approximately 150 to 500 /square. Different connections between conductive fabrics and the power source were examined. When subjected to a constant voltage of 24 V, the current transmitted through the fabric decreased about 10% in 72 h. An increase in resistance of conductive fabrics subjected to constant voltage was observed

The effects of dye dopants on the conductivity and optical absorption properties of polypyrrole

Ten anionic compounds, including four acidic dyes, were used to dope polypyrrole powder. The effects of the dopants on density, optical absorption and conductivity of the polypyrroles were studied. The presence of the dopant in the conducting polymer matrix was verified by ATR-FTIR spectroscopy. Density function theory (DFT) simulation was used to understand the effect of the dopants on the solid structure, optical absorption and energy band structures. Anthraquinone-2-sulfonic acid-doped polypyrrole yielded the highest conductivity. The dye-doped polypyrrole showed an enhancement in its UV–vis optical absorption.

Use of ionic liquids as electrolytes in electromechanical actuator systems based on inherently conducting polymers

The use of ionic liquids (ILs) as electrolytes for electromechanical actuators based on polypyrroles (PPy's) is described. The composition of the electrolytes has a significant effect on the electrochemical properties of the PPy actuator and subsequently on actuator performance, improving cycle life and strain generated. The actuator performance in ionic liquid electrolytes is significantly better than that in traditional organic and aqueous electrolytes.

Structural characterization of conducting polypyrrole using 13C cross-polarization/magic-angle spinning solid-state nuclear magnetic resonance spectroscopy

¹³C nuclear magnetic resonance (n.m.r.) has been used to study polypyrrole and N-substituted polypyrrole in the solid state. The extent of oxidation appears to be counterion-dependent; in particular, the quinoid structure appears favoured in the films prepared with dodecyl sulfate. Resonances associated with the quinoid unit are lost upon reduction of the polypyrrole film, which supports the idea that the quinoid structure is associated with the oxidized form of polypyrrole. N-substituted polypyrroles have a more distinct resonance at 110 ppm, which is linked to lower degrees of oxidation or charge delocalization in these systems. The decrease in conductivity of polypyrrole upon thermal ageing in air is associated with both the loss of counterion (‘thermal dedoping’) and the decomposition of the quinoid structure in the polymer backbone. There is no indication of carbonyl formation in the solid-state n.m.r. spectra obtained in the present study.

Synthesis and characterization of soluble conducting polymers

Although conducting polymers have various potential applications, lack of solubility is an impediment in their direct application to material surfaces. Synthesis of alkyl pyrrole monomers and subsequent polymerization into soluble conducting polymers are aimed as alternatives to conventional methods of application of conducting polymers on substrates. Alkyl chains are attached to a pyrrole ring to produce solubility in the resulting conducting polypyrroles, which allow direct application of conductive polymer emulsions to any desired surface. Friedel-Crafts acylation of the tosyl-protected pyrrole provides high yields of the 3-acylated product. The conductivity values of poly-3- and 3, 4-substituted pyrroles are generally less than the unmodified polypyrrole. Increasingly bulkier groups attached to the pyrrole means lower conductivity of the resultant polymer. As the carbon chain length attached to the 3-position of pyrrole increases, the solubility also increases. However, the magnitude of change in conductivity of films and pellets of soluble conducting polypyrroles over the alkyl range is not significant.

Synthesis of 2-(selenophen-2-yl) pyrroles and their electropolymerization to electrochromic nanofilms

The divergent syntheses of 2-(selenophen-2-yl)pyrroles and their N-vinyl derivatives from available 2-acylselenophenes and acetylenes in a one-pot procedure make these exotic heterocyclic ensembles accessible. Now we face a potentially vast area for exploration with a great diversity of far-reaching consequences including conducting electrochromic polymers with repeating of pyrrole and selenophene units (emerging rivalry for polypyrroles and polyselenophenes), the synthesis of functionalized pyrrole–selenophene assembles for advanced materials, biochemistry and medicine, exciting models for theory of polymer conductivity.