Efficient synthesis of EDOT modified ABBB-type unsymmetrical zinc phthalocyanine: Optoelectrochromic and glucose sensing properties of its copolymerized film

A new unsymmetrical zinc(ii) phthalocyanine (ZnPc2) bearing one EDOT group was efficiently synthesized as a monomer through the statistical condensation reaction. The other products of mixed cyclotetramerization ZnPc1, ZnPc3 and ZnPc4 were also isolated. Obtained ZnPc2 is a good precursor for the synthesis of new functional linear electropolymers. This was approved by the successful electrochemical copolymerization reaction between ZnPc2 and SNS type monomer HKCN in which the amino group was desired for the enzyme immobilization. The electrochromic and glucose sensing properties of copolymer P(ZnPc2-co-HKCN) obtained by electrochemical oxidative polymerization were investigated. Based on spectroelectrochemical studies, the P(ZnPc2-co-HKCN) copolymer showed a greenish yellow colour in the reduced state and a dark blue colour in the oxidized state as a film. An optical contrast ratio of 44% at 471 nm was achieved with a fast switching time (2.5 s). Meanwhile, the novel biosensor constructed from P(ZnPc2-co-HKCN) showed a linear amperometric response to glucose within a concentration range of 0.1 mM to 1.5 mM (LOD: 0.049 mM). These data illustrate the possible use of the P(ZnPc2-co-HKCN) modified electrode as an amperometric glucose sensor. © 2017 The Royal Society of Chemistry and the Centre National de la Recherche Scientifique

High contrast electrochromic polymer and copolymer materials based on amide-substituted poly(dithienyl pyrrole)

Conducting polymers have attracted attention as active materials for low power consuming, flexible devices with vivid colors and simple, room temperature processing methods. However, the conductive polymers with high-contrast electrochromic properties are limited in the literature. Here we achieve high-contrast electrochromic switching by copolymerization of newly synthesized an amide substituted dithienyl pyrrole (PBA) and 3,4-ethylenedioxythiophene (EDOT). In order to obtain the best optical properties of copolymer, spectral characteristics of the synthesized copolymers with different monomer feed ratios were investigated. Both homopolymer and copolymer films exhibit well defined redox and satisfied coloration efficiency. Spectroelectrochemistry studies indicate that the P(PBA-co-EDOT) has a lower bandgap (1.67 eV) and shows the excellent optical contrast (77% of 1000 nm) and coloration efficiency (697.01 cm2 C-1). The copolymer method provides a novel way to fabricate a freestanding organic electrochromic device. Additionally, the fluorescence properties of both monomer and polymer were investigated. P(PBA) having strong emission and good solubility and also P(PBA) has the potential to be used in OLEDs. © 2016 The Electrochemical Society. All rights reserved