To investigate the counter ion diffusivity of polymers with intrinsic microporous structures during the electrochemical process, Tröger's base (TB) with a non-planar and V-shaped moiety was introduced to facilitate the formation of diffusion channels. The TB-incorporated polyamides (TPPA-TB and TPPA-Me-TB) revealed enhanced electrochromic properties due to higher diffusivity, which could effectively narrow down the electrochemical redox potential difference (ΔE), resulting in a higher switching response speed (υ) while maintaining similar transmittance change (ΔT). Intriguingly, the triarylamine-based polyamide TPPA-Me-TB demonstrated excellent charge–discharge ability with a high specific capacitance (C_sp) of 165.3 F g⁻¹ at 1.0 A g⁻¹ and distinct two-stage color changes from colorless to green (0.8 V) and to blue (1.2 V), which could monitor the content of charge capacity. Therefore, these novel redox-active polyamides should be attractive and suitable for electrochromic supercapacitor (ECS) materials.

A highly atom-economic AB ₂ -type hyperbranched polyamide, HPA-TPA, was judiciously designed and prepared. HPA-TPA showed remarkable electrochromic behaviours and charge–discharge characteristics with the aid of the hyperbranched architecture.