Fine-Tuning the Color Hue of π-Conjugated Black-to-Clear Electrochromic Random Copolymers

A family of dioxythiophene (DOT)-based conjugated random copolymers, capable of reversibly switching between a neutral black and an oxidized transmissive state, are reported for electrochromic (EC) applications. By replacing 3,4-ethylenedioxythiophene (EDOT) in the previous generation of a core donor–acceptor–donor (D–A–D) terheterocycle with a methyl-alkylated 3,4-propylenedioxythiophene (ProDOT), we enhance the solubility of precursors and monomers in this new generation of broadly absorbing electrochromic polymers (ECPs). By adjusting the newly designed terheterocycle monomer feed ratio, we obtain three polymers with varying hues of color neutrality (a* and b* < ±10) throughout the entire switching voltage range and with integrated contrasts 45–49% throughout the visible region (380–700 nm). The a* values of the polymers ranged between −8 (green hue) and +5 (red hue), with their b* values ranging between −4 and −7 (blue hue) in their neutral states; additionally, the a* and b* values are all below ±8 i...