Shao, Yu‐JenYu‐JenShaoLin, Chin‐HsuanChin‐HsuanLinChang, Cha‐WenCha‐WenChangKao, Yu‐TingYu‐TingKaoHo, Hung‐LinHung‐LinHoMizuno, RyuhoRyuhoMizunoShimizu, MasakiMasakiShimizuGUEY-SHENG LIOU2025-08-142025-08-142025-07-20https://www.scopus.com/record/display.uri?eid=2-s2.0-105010873313&origin=resultslisthttps://scholars.lib.ntu.edu.tw/handle/123456789/731393Electrochromic materials could modulate optical properties via applied voltage and are integral to smart windows, displays, and energy-efficient devices. This study presents molecule-engineered triarylamine-based non-conjugated polyamide (A-NCP) for multifunctional optoelectrochemical and energy-saving applications. Four polyamides are synthesized, and all exhibited excellent electrochromic behaviors and properties. Among them, the terephthalamide-bridge triarylamine polyamide reveals a significant bathochromic shift of nearly 300 nm compared to the conventional phenyl π-bridge in the cation radical form, extending intervalence charge-transfer (IV-CT) absorption into the NIR-II region (1246 nm) and demonstrating broadband absorption across visible to NIR-II wavelengths, high optical contrast ratios, and rapid response times. Notably, it enables monitoring residual capacity via absorption changes via blue, orange, NIR-I, and NIR-II light sources in electrochromic supercapacitors. Beyond light-absorption monitoring, light-emission monitoring could also be achieved by integrating electrofluorochromism with supercapacitors, enabling whole-day monitoring capabilities. Furthermore, broadband NIR absorption effectively suppresses heat penetration and mitigates water temperature which increases from 11.2 °C to only 3.2 °C at room temperature and atmospheric pressure. These findings position these molecule-engineered terephthalamide-bridge triarylamine derivatives as promising materials for up-and-coming next-generation multifunctional optoelectrochemical and energy-saving applications.truebroadband NIR adsorptionselectrochromic supercapacitorselectrochromismelectrofluorochromismheat-shielding[SDGs]SDG7journal article10.1002/sstr.2025003572-s2.0-105010873313