Dual Stimuli‐Responsive [2]Rotaxanes with Tunable Vibration‐Induced Emission and Switchable Circularly Polarized Luminescence

Abstract Aiming at the construction of novel stimuli‐responsive fluorescent system with precisely tunable emissions, the typical 9,14‐diphenyl‐9,14‐dihydrodibenzo[a, c]phenazine (DPAC) luminogen with attractive vibration‐induced emission (VIE) behavior has been introduced into [2]rotaxane as a stopper. Taking advantage of their unique dual stimuli‐responsiveness towards solvent and anion, the resultant [2]rotaxanes reveal both tunable VIE and switchable circularly polarized luminescence (CPL). Attributed to the formation of mechanical bonds, DPAC‐functionalized [2]rotaxanes display interesting VIE behaviors including white‐light emission upon the addition of viscous solvent, as evaluated in detail by femtosecond transient absorption (TA) spectra. In addition, ascribed to the regulation of chirality information transmission through anion‐induced motions of chiral wheel, the resolved chiral [2]rotaxanes reveal unique switchable CPL upon the addition of anion, leading to significant increase in the dissymmetry factors ( g lum ) values with excellent reversibility. Interestingly, upon doping the chiral [2]rotaxanes in stretchable polymer, the blend films reveal remarkable emission change from white light to light blue with significant 6.5‐fold increase in g lum values up to −0.035 under external tensile stresses. This work provides not only a new design strategy for developing molecular systems with fluorescent tunability but also a novel platform for the construction of smart chiral luminescent materials for practical use.