Highly Stable Indacenodithieno[3,2-b]thiophene-Based Donor-Acceptor Copolymers for Hybrid Electrochromic and Energy Storage Applications.

Stable doping of indacenodithieno[3,2-b]thiophene (IDTT) structures enables easy color tuning and significant improvement in the charge storage capacity of electrochromic polymers, making use of their full potential as electrochromic supercapacitors and in other emerging hybrid applications. Here, the IDTT structure is copolymerized with four different donor-acceptor-donor (DAD) units, with subtle changes in their electron-donating and electron-withdrawing characters, so as to obtain four different donor-acceptor copolymers. The polymers attain important form factor requirements for electrochromic supercapacitors: desired switching between achromatic black and transparent states (L*a*b* 45.9, -3.1, -4.2/86.7, -2.2, and -2.7 for PIDTT-TBT), high optical contrast (72% for PIDTT-TBzT), and excellent electrochemical redox stability (Ired/Iox ca. 1.0 for PIDTT-EBE). Poly[indacenodithieno[3,2-b]thiophene-2,8-diyl-alt-4,7-bis(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-2-(2-hexyldecyl)-2H-benzo[d][1,2,3]triazole-7,7'-diyl] (PIDTT-EBzE) stands out as delivering simultaneously a high contrast (69%) and doping level (>100%) and specific capacitance (260 F g-1). This work introduces IDTT-based polymers as bifunctional electro-optical materials for potential use in color-tailored, color-indicating, and self-regulating smart energy systems.