Applications of Three Dithienylpyrroles-Based Electrochromic Polymers in High-Contrast Electrochromic Devices

Three dithienylpyrroles (1-(4-(methylthio)phenyl)-2,5-di(thiophen-2-yl)-pyrrole (MPS), 1-(4-methoxyphenyl)-2,5-di(thiophen-2-yl)-pyrrole (MPO), and 4-(2,5-di(thiophen-2-yl)-pyrrol-1-yl)benzonitrile (ANIL)) were synthesized and their corresponding polydithienylpyrroles (PSNS) were electrosynthesized using electrochemical polymerization. Spectroelectrochemical studies indicated that poly(1-(4-(methylthio)phenyl)-2,5-di(thiophen-2-yl)-pyrrole) (PMPS) film was green, dark green, and brown in the neutral, oxidation, and highly oxidized state, respectively. The incorporation of a MPS unit into the PSNS backbone gave rise to a darker color than those of the MPO and ANIL units in the highly oxidized state. The PMPS film showed higher ΔT_max (54.47% at 940 nm) than those of the PMPO (43.87% at 890 nm) and PANIL (44.63% at 950 nm) films in an ionic liquid solution. Electrochromic devices (ECDs) employing PMPS, PMPO, and PANIL as anodic layers and poly(3,4-(2,2-diethypropylenedioxy)thiophene)(PProDOT-Et₂) as a cathodic layer were constructed. PMPO/PProDOT-Et₂ ECD showed the highest ΔT_max (41.13%) and coloration efficiency (674.67 cm²·C^-¹) at 626 nm, whereas PMPS/PProDOT-Et₂ ECD displayed satisfactory ΔT_max (32.51%) and coloration efficiency (637.25 cm²·C^-¹) at 590 nm. Repeated cyclic voltammograms of PMPS/PProDOT-Et₂, PMPO/PProDOT-Et₂, and PANIL/PProDOT-Et₂ ECDs indicated that ECDs had satisfactory redox stability.