Journal of Polymer Science Part A Polymer Chemistry · 1997 · 38 citations · 0 references
Natural SciencesChemistryMaterials ScienceElectrochemistryOrganic ChemistryPolymer ChemistryConducting PolymersConductive PolymersOrganic Electronic MaterialsPolymer Physical ChemistryPolymer Thin FilmsPolymerization ChemistryConducting Polymer SynthesisElectrochemical PotentialsElectron-donating GroupsFilm DepositionReactivityStabilization In Organic SolventsSynthesis Of Conducting Polymers
The monomers bis(2‑thienyl)-9,9‑didecylfluorene (BTDF) and bis(3,4‑(ethylenedioxy)thien‑2‑yl)-9,9‑didecylfluorene (BEDOT‑DF) were synthesized and electropolymerized to yield conducting polymers. Electropolymerization of BTDF depends on solvent composition, occurring only above 1.3 V in CH₂Cl₂ but efficiently at 0.9 V in a 30/70 CH₂Cl₂/CH₃CN mixture, whereas BEDOT‑DF polymerizes more rapidly at 0.55 V due to alkoxy‑induced stabilization of cation radicals; the resulting neutral polymers are insoluble, thermally stable to 300 °C, exhibit conductivities up to 10⁻⁴ S cm⁻¹, show bipolaronic intragap transitions upon oxidation, and display ion transport dominated by electrolyte anions. © 1997 John Wiley & Sons, Inc., J Polym Sci A: Polym Chem 35: 3627–3636.
The monomers bis(2-thienyl)-9,9-didecylfluorene, BTDF, and bis(3,4-(ethylenedioxy)thien-2-yl)-9,9-didecylfluorene, BEDOT-DF, have been synthesized and electropolymerized to the corresponding conducting polymers. The potential for the electropolymerization of BTDF was found to be dependent on the solvent composition. In CH2Cl2, polymer film deposition is achieved only at potentials higher than 1.3 V vs. Ag/Ag+, while in a 30/70 mixture of CH2Cl2/CH3CN the polymerization is efficient at 0.9 V. BEDOT-DF polymerizes at significantly lower potentials and more rapidly than BTDF. The electron-donating alkoxy substituents of the EDOT units lead to stabilization of the cation radical intermediates allowing the electropolymerization to proceed at 0.55 V. The neutral polymers are insoluble in common organic solvents and are stable to 300°C under nitrogen. Upon oxidation, both polymers show two intragap transitions at intermediate doping levels due to the formation of bipolaronic states and the oxidized polymers exhibit conductivities up to 10−4 S/cm. The redox-stimulated ion transport characteristics, studied by the electrochemical quartz crystal microbalance (EQCM) indicates that the electrolyte anions are the dominant mobile species. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3627–3636, 1997