Synthesis, electropolymerization and characterization of a cross-linked PEDOT derivative

Journal ar
Journal of Materials Chemistry
  • Volumen: 22
  • Número: 11
  • Fecha: 21 marzo 2012
  • Páginas: 4944-4952
  • ISSN: 09599428 13645501
  • Tipo de fuente: Revista
  • DOI: 10.1039/c2jm14909e
  • Tipo de documento: Artículo
The synthesis of a novel electropolymerizable monomer, 2,2¿,3, 3¿-tetrahydro-2,2¿-bithieno[3,4-b][1,4]dioxine (THBTD), based on two 3,4-ethylenedioxythiophene (EDOT) moieties connected through the ethylenedioxy bridge is reported. The new monomer paves the way for the development of cross-linked networks based on the EDOT moiety. Polymer films were electrogenerated from monomeric solutions by consecutive potential sweeps or by flow of constant anodic currents and the polymer structure was studied using FTIR. The relationship between the mass of the electrogenerated polymer (after reduction) and the polymerization charge gives the productivity of the consumed charge (mg C -1) while the charge stored and delivered by the films was determined by cyclic voltammetry getting the specific charge (C g -1). Simultaneously with the electroinitiated polymerization a chemical polymerization occurs around the electrode by monomer protonation giving protonated and no electroactive polymer chains. This chemical polymerization was followed in solution by UV-Vis spectroscopy using different conditions. Productivities and specific charges change with the conditions of synthesis in opposite directions. The voltammetric control presents a main redox couple (0.54/0.50 V) and a strong reduction process at -2.89 V that only can be reoxidized at more anodic potentials than 0.3 V as usual for charge trapping effects. EQCM studies indicate a remarkable difference between PEDOT and poly(THBTD). While poly(THBTD) shows a predominantly reversible anionic exchange during oxidation from the neutral state, the parent pristine PEDOT presents a mixed anionic and cationic exchange. Electrochromic color changes from an intense blue color of the oxidized film to a clear orange color in the reduced films as observed by in situ UV-Vis spectroscopy. Interestingly, the electrochromic changes in poly(THBTD) are opposed to those of PEDOT. Both thiophene derivative polymers present a similar thermal degradation at 305 and 314 °C, respectively. © 2012 The Royal Society of Chemistry.

Palabras clave del autor

    Palabras clave indexadas

      Detalles de financiación