DNA-inspired self-complementary architecture: Achieving stable decoupling of thermodynamic and optical properties in polyimides through orchestrated hydrogen bonding

DNA achieves the most stable molecular recognition and information storage system in nature by integrating structural artistry with functionality. Inspired by this, we developed a biomimetic strategy based on azaindole-modified diamines to construct self-complementary hydrogen bond networks in polyimides. This approach transforms conventional donor–acceptor chain stacking into donor–donor configurations. The DNA base-pairing-like molecular design significantly reduced the cutoff wavelengths in polyimide (>35 nm blue shift), while maintaining excellent thermodynamic stability (Td^5% > 550 °C and CTE_50-350°C: 15.4–33.6 ppm·K⁻¹). The resulting materials exhibit exceptional electrical performance stability. The ketone-containing polyimide achieved outstanding breakdown strength (585.6 MV/m), while the ether-containing polyimide delivered high energy density (2.46 J/cm³ at 350 MV/m with 85 % efficiency). This “geometric blocking-dynamic reinforcement” mechanism enables stable property decoupling in polyimides, providing a practical design strategy for high-performance polyimide materials with simultaneously enhanced optical transparency and thermomechanical properties for flexible optoelectronic applications.