Viologen‐based host–guest supramolecule with tunable intramolecular/intermolecular electron transfer chromism and dynamic fluorescence

Abstract Viologen, as a type of strong electron acceptor, is prone to undergo electron transfer (ET) and change color under external stimuli. However, due to the easy aggregation of viologen molecules, they usually suffer from poor fluorescence emission in the condensed phase. Herein, a new viologen derivative of VioCl 2 ·2Cl ( 1 2+ ·2Cl) was designed and synthesized, in which the fluorescence was enhanced by introducing Me‐β‐CD to weaken the interactions between viologen molecules. Then a viologen‐based host–guest supramolecule of 1 2+ @Me‐β‐CD was obtained by electrostatic interactions. Photo‐/chemo‐responded guest 1 2+ supplies 1 2+ @Me‐β‐CD , a green and dark purple caused by intramolecular and intermolecular ET. Furthermore, 1 2+ @Me‐β‐CD displays an additional thermal responsive purple color. The triple chromic behaviors all exhibit excellent reversibility and cycling stability. As expected, 1 2+ @Me‐β‐CD exhibits strong photoluminescence (PL) in solid–liquid dual states, presenting an improved quantum yield (Φ) from 1 2+ (Φ s = 0.37%, Φ l = 16.74%) to 1 2+ @Me‐β‐CD (Φ s = 10.45%, Φ l = 25.86%), and the fluorescence intensity can be dynamically modulated by light, heat, and acid/base vapors. The multi‐responsive chromism and tunable fluorescence of 1 2+ @Me‐β‐CD allow for potential applications in information security and smart windows.