Asymmetric Bis‐Dipolar Chromophore Design Enables Multi‐Route Multi‐Color Photochromism and Solid‐State Thermochromism

Abstract Donor‐acceptor Stenhouse adducts (DASAs) are newly‐emerged organic photoswitches, but developing multi‐faceted complex responsive systems beyond conventional binary responses remains challenging. Unlike popular dipolar molecule design, a novel asymmetric bis‐dipolar (A‐D‐A) chromophore design is proposed to produce a new family of dual‐stimuli‐responsive Stenhouse system, namely ADASA, that displays multi‐route multi‐colored visible‐light photochromism and solid‐state thermochromism in one molecule‐never attained in previous Stenhouse compound. The optimized ADASA 3 features bi‐branched structures where two dipolar chromophores with less absorption overlap are connected via a decoupled linkage. This decoupling is confirmed to be achieved by modulating the linkage to increase the dihedral angle between the chromophores. Such a design can retain the intrinsic switching behavior of two chromophores while exerting their synergistic effects and responsive difference to enable complex multi‐responsive behavior beyond simple two‐state transition and single optical control. Specifically, ADASA 3 achieves multiple optical wavelength controls for fast four‐colored variation (blue, green, purple, and colorless) in solution and affords rapid thermos‐induced purple‐to‐blue transition in polymer films upon heating at 60 °C. Mechanism studies underscore the pivotal role of asymmetric A‐D‐A structure and decoupled linkage toward intriguing multi‐responsive ability. ADASA 3 shows significant potential for applications in multi‐route logic gates, information encryption, and thermochromic patterning.