Electrochromic (EC)/electrofluorochromic (EFC) bifunctional materials are receiving great attention because of their promising applications in optoelectronic devices. However, the development of ideal EC/EFC bifunctional materials is still a great challenge because of the poor integration of EC/EFC performances (optical contrast, response speed, and switching stability). Herein, we reported two novel diphenylamine-based mixed valence (MV) polyamides (S-HPA and P-HPA) with spirobifluorene (2,7-positions) and pyrene (1,6-positions) as bridged fluorescence units, respectively, showing impressive cyclability and fluorescence contrast with rapid switching. Through the formation of an effective electronic coupling between the two nitrogen centers using spirobifluorene/pyrene bridges, we demonstrated that different bridges have significant effects on the thermal and electrooptical characteristics of polyamides. In addition to lower fluorescence quantum yield and glass transition temperature, the S-HPA exhibited superior cyclability (contrast change <3.4%/14% over 500/300 cycles for EC/EFC switching), higher color/fluorescence contrast (64%/304%), and faster switching time (<2.6 s), mainly owing to the shorter conjugated length and more twisted configuration of the spirobifluorene bridge. The design principle of MV polymers with fluorophore bridges proposed here will be a promising way to realize high-performance EC/EFC devices and will also provide new insights into their future development and applications.

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A novel EC/EFC polyamide is realized by introducing stably electroactive p-phenylenediamine and asymmetrical SBF/TPA-based unit to reduce packing.