Prolonged storage (~2 years) or gentle heating (50-80
![](/images/entities/deg.gif)
C) of crystalline 2,5-dibromo-3,4-ethylenedioxythiophene (DBEDOT) affords a highly conducting, bromine-doped poly(3,4-ethylenedioxythiophene) (PEDOT), as confirmed by solid-state NMR, FTIR, CV, and vis-NIR spectroscopies. The novelsolid-state polymerization (SSP) does not occur for 2,5-dichloro-3,4-ethylenedioxythiophene (DCEDOT),and requires a much higher temperature (>130
![](/images/entities/deg.gif)
C) for 2,5-diiodo-3,4-ethylenedioxythiophene (DIEDOT).X-ray structural analysis of the above dihalothiophenes reveals short Hal···Hal distances between adjacentmolecules in DBEDOT and DIEDOT, but not in DCEDOT. The polymerization may also occur in the meltbut is significantly slower and leads to poorly conductive material. Detailed studies of the reaction wereperformed using ESR, DSC, microscopy, and gravimetric analyses. SSP starts on crystal defect sites; it isexothermic by 14 kcal/mol and requires activation energy of ~26 kcal/mol (for DBEDOT). The temperaturedependence of the conductivity of SSP-PEDOT (
rt = 20-80 S/cm) reveals a slight thermal activation. Itcan be further increased by a factor of 2 by doping with iodine. Using this approach, thin films of PEDOTwith conductivity as high as 20 S/cm were fabricated on insulating flexible plastic surfaces.