Low‐oxidation‐potential conducting polymers derived from 3,4‐ethylenedioxythiophene and dialkoxybenzenes

Abstract

Monomers derived from 3,4‐ethylenedioxythiophene and phenylenes with branched or oligomeric ether dialkoxy substituents were prepared with the Negishi coupling technique. Electrooxidative polymerization led to the corresponding dialkoxy‐substituted 3,4‐ethylenedioxythiophene–phenylene polymers, with extremely low oxidation potentials (E1/2,p = −0.16 to −0.50 V vs Ag/Ag+) due to the highly electron‐rich nature of these materials. The polymers were electrochromic, reversibly switching from red to blue upon oxidation, with bandgaps at about 2 eV. The electrochemical behavior of the oligomeric ether‐substituted polymer was investigated in the presence of different metal ions. Films of the polymer exhibited electrochemical recognition for several alkali and alkaline‐earth cations with selectivity in the order Li+ > Ba2+ > Na+ > Mg2+. Cyclic voltammetry showed a decrease in the oxidation potential and an improvement in the definition of the voltammetric response, as well as an increase in the overall electroactivity of the polymer films when the concentration of the cations in the medium was increased. These results are discussed in terms of the electrostatic interactions between the complexed cation and the redox center, as well as the diffusion of the ionic species into the polymer matrix. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2164–2178, 2001

Design, synthesis and electrochemical properties of a thiophene derivative functionalized with a siderophore-like chelator

“…The rapid saturation of the OCP can be attributed to the formation of a silver film at the surface electrode due to the reduction of Ag + during polymer backbone oxidation. This phenomenon was already described for the oxidation of PEDOT with Ag + [9]. Due to this silver film the efficiency of the polymer oxidation process decreases and leads to a quasi stable OCP value.…”

A Highly Stable, New Electrochromic Polymer: Poly(1,4‐bis(2‐(3′,4′‐ethylenedioxy) thienyl)‐2‐methoxy‐5‐2″‐ethylhexyloxybenzene)

“…[33,34] Alternatively, the monomer can also be synthesized by Grignard coupling reactions, as reported by the Reynolds group in the synthesis of a series of 1,4-bis(2-thenyl)-phenylenes, and bis(3,4-ethylenedioxythiophene)benzene. [35,36] The organotin compound I was readily obtained in high yield by direct lithiation of an equal molar ratio of 3,4-ethylenedioxythiophene, followed by reaction with stannyl chloride. The dibromo compound II was synthesized by bromination of the corresponding asymmetric alkyloxy-substituted phenyl compound.…”

Electrochromic organic and polymeric materials for display applications

“…Using a series of oxidatively polymerizable bisarylene EDOT monomers (figure 9), polymers with bandgaps ranging from 1.4 -2.5 eV have been prepared that exhibit two to three distinct colored states. 75,76,[95][96][97] FIGURE 9…”