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A series of copolymers containing a glycolated 1,4‐dithienyl‐2,3,5,6‐tetrafluorophenylene unit copolymerized with thiophene, bithiophene, thienothiophene and 1,2,4,5‐tetrafluorobenzene comonomer units were designed and synthesised by direct heteroarylation polymerisation. The optical, electrochemical, electrochromic and solid‐state structural properties of the copolymers were investigated. The copolymers exhibit stable redox properties in organic solvents and promising redox properties in thin film configuration with an aqueous electrolyte. Finally, the potential of the copolymers as active materials in organic electrochemical transistors (OECTs) was assessed, and promising performance was shown as an accumulation‐mode OECT material with a peak transconductance of 0.17 mS and a good on/off ratio of 105 for the thiophene copolymer. [ABSTRACT FROM AUTHOR]

This study reports the synthesis and characterization of poly(3-hexylthiophene) (P3HT) from a direct heteroarylation polymerization of two isomeric monomers, 2-bromo-3-hexylthiophene (monomer 1) and 2-bromo-4-hexylthiophene (monomer 2). Using the Herrmann-Beller catalyst along with P(o-NMe2Ph)3, the resulting polymers are obtained in excellent yields and exhibit a good number-average molecular weight (Mn of 33 and 16 kDa, respectively). Detailed ¹H NMR analyses reveal less than 1% of homocouplings and no evidence of β-branching. Dehalogenation is identified as the main chain termination step and preferentially occurs on monomer 2. The melting temperature (237 °C) and hole mobility (up to 0.19 cm² V-1⋅s-1) of the nearly defect-free P3HT obtained from this simple polymerization of monomer 1 are comparable, if not superior, to those obtained with commercially available GRIM and Rieke samples. [ABSTRACT FROM AUTHOR]