Low potential electrodeposition of high‐quality and freestanding poly(3‐(6‐bromohexyl)thiophene) films

Abstract

High-quality freestanding and conducting poly [3-(6-bromohexyl)thiophene] (PBHT) films with electrical conductivity of 20 S/cm were synthesized electrochemically by direct anodic oxidation of 3-(6-bromohexyl)thiophene (BHT) in boron trifluoride diethyl etherate (BFEE). The oxidation potential of BHT in pure BFEE was measured to be only 1.2 V versus saturated calomel electrode, SCE much lower than that determined in acetonitrile (ACN) (1.8 V vs SCE). The polymer films obtained from this media were very shiny and flexible and can be easily cut into various shapes. The structure and morphology of the polymer films were investigated by UV-vis, infrared, 1 H-NMR spectroscopy, thermal analysis, and scanning electron microscopy (SEM). All these results indicated that the terminal bromide did not have negative effect on the electrochemical polymerization of BHT.

Dye-sensitized solar cells (DSSCs) based on poly(3-hexylthioacetate thiophene)

“…The protons of the side chain (6-hexylbromide) in Compound [11] had remained unchanged in Compound [12] suggesting that the side chain is stable to the postpolymerization conditions. This result is similar to those reported by other workers for similar polymers (Zhai et al, 2003;Xu et al, 2008). The presence of a singlet at δ 2.32 ppm due to 3-hydrogen atoms in the spectra of Compound [12] could indicate the presence of methyl group attached to a carbonyl group (Figure 5).…”

Polyfluorene Derivatives with Hydroxyl and Carboxyl Substitution: Electrosynthesis and Characterization

“…The main reason for the unsatisfactory properties is that the potential applied for polymerization is much higher than the reversible redox potential of the PFs, resulting in destruction of the conjugated structure of the polymers and degradation of their properties . Recently, our research group reported that the quality of PF films can be improved using boron trifluoride diethyl etherate (BFEE) as the solvent and supporting electrolyte because of its catalytic effect. – Moreover, BFEE has been found to be an excellent electrolyte for the electrochemical polymerization of other compounds such as benzene and thiophene, – especially for fused-ring compounds such as indole, carbazole, naphthalene, and their derivatives. – High-quality conjugated polymer films can be obtained from this electrolyte.…”

Electrosyntheses of free-standing poly(thiophene-3-acetic acid) film in mixed electrolytes of boron trifluoride diethyl etherate and trifluoroacetic acid

“…These differences between the doped and dedoped PTAA films were mainly due to the migration of counteranion out of the polymer film and the gradual solubility of oligomer from the electrode to the solution during the dedoping proesses, which broke the smooth surface of the doped PTAA film. The conductivity of the doped PTAA film obtained from BFEE + 25% TFA was measured to be 7 S cm −1 , which was similar to the value of poly(3-(6-Bromohexyl)Thiophene) (20 S cm −1 ) [40] , higher than the value of poly(3-chlorothiophene) (0.1 S cm −1 ) [27] , poly(3-phenylthiophene) (0.01 S cm −1 ) [44] and poly(3-methoxythiophene) (3.8 S cm −1 ) [41] . Additionally, the electrical conductivity of dedoped PTAA film was measured to be 10 −6 S cm −1 .…”

“…7(a), three peaks at δ = 7.13, 6.89, and 6.78 are assigned to the protons at the C(2), C(3), and C(5) positions (in the inset of Fig. 7), respectively [40,41] . In the same region, there is only one broad peak at δ = 6.98 for the polymer, corresponding to the C-H bond at the C(3) position.…”