Metal‐Free Hybrid Energetic Composites Based on Donor–Acceptor π‐Conjugated Organic Energetic Catalysts with Enlightening the Laser Ignition Performance of Multi‐Scale Ammonium Perchlorate

Abstract Photosensitive materials, such as energetic complexes, usually have high sensitivity and cause heavy‐metal pollution, whereas others, like carbon black and dye, do not contain energy, which affects energy output and mechanical properties. In this work, donor–acceptor π‐conjugated energetic catalysts, denoted as D‐n, are designed and synthesized. Nonmetallic hybrid energetic composites are prepared by assembling the as‐synthesized catalysts into multiscale ammonium perchlorate (AP). Composites containing catalysts and APs can be successfully ignited without the involvement of metals. The new ignition mechanism is further analyzed using experimental and theoretical analyses such as UV–vis‐near‐infrared (NIR) spectra, electron‐spin resonance spectroscopy, and energy‐gap analysis. The shortest ignition delay time is 56 ms under the experimental condition of a NIR wavelength of 1064 nm and a laser power of 10 W. At the voltage of 1 kV and the electric field of 500 V mm⁻¹, the laser‐ignition delay time of D‐2/AP hybrid composite decreases from 56 to 35 ms because D‐2 also exhibits organic semiconductor‐like properties. D‐2/AP and D‐12/AP can also be used to successfully laser ignite other common energetic materials. This study can guide the development of advanced metal‐free laser‐ignitable energetic composites to address challenges in the field of aerospace engineering.