On‐Substrate Preparation of an Electroactive Conjugated Polyazomethine from Solution‐Processable Monomers and its Application in Electrochromic Devices

Abstract An electroactive polyazomethine is prepared from a solution processable 2,5‐diaminothiophene derivative and 4,4′‐triphenylamine dialdehyde by spray‐coating the monomers on substrates, including indium tin oxide (ITO) coated glass and native glass slides. The conjugated polymer was rapidly formed in situ by heating the substrates at 120 °C for 30 min in an acid saturated atmosphere. The resulting immobilized polymer is easily purified by rinsing the substrate with dichloromethane. The on‐substrate polymerization is tolerant towards large stoichiometry imbalances of the comonomers, unlike solution step‐growth polymerization. The resulting polyazomethine is electroactive and it can be switched reversibly between its neutral and oxidized states both electrochemically and chemically without degradation. A transmissive electrochromic device is fabricated from the immobilized polyazomethine on an ITO electrode. The resulting device is successfully cycled between its oxidized (dark blue) and neutral (cyan/light green) states with applied biases of +3.2 and ‐1.5 V under ambient conditions without significant color fatigue or polymer degradation. The coloration efficiency of the oxidized state at 690 nm is 102 cm² C⁻¹.