Two new donor-acceptor (D-A) type organic conjugated random copolymers were successfully synthesized by three-component Stille coupling polymerization of indolo[3,2-b]carbazole (ICZ), isoindigo (IID) and thiophene units, namely PITID-X (X = 1 and 2), with the controlled monomer feed ratios of 3:1:4 and 1:1:2, respectively. The strategy of incorporating different alkyl-branched donor/acceptor units and raw material feed ratios facilitated the improvement of optical properties, solubility, conjugated structure, and electrochromic performance. Cyclic voltammetry, UV-vis-NIR absorption spectra, kinetic and colorimetric measurements of the spray-coated films were recorded in the fabricated three-electrode cells. The results showed that PITID-2, whose optical/electrical properties were better than that of PITID-1, was the candidate electrochromic material due to low band gap of 1.58 eV accompanying the color changing from cyan (neutral state) to gray (oxidized state). The copolymer also illustrated fast bleaching/coloration response time of 2.04/0.33 and 1.35/1.50 s in a 4 s time interval, high coloration efficiency of 171.52 and 153.08 cm2 C-1 and stable optical contrast of 18% and 58% at the wavelength of 675 and 1600 nm, respectively.
Keywords: Indolo[3,2-b]carbazole; conjugated polymers; electrochromism; isoindigo; stille coupling.