Exploring Green Pyrotechnic Formulations and Primary Explosives with 1,3,4‐Oxadiazole‐Based Micro and Submicron Energetic Coordination Polymers

Abstract Alkali and alkaline‐earth metal incorporated 5,5′‐dinitramino‐3,3′‐azo‐1,3,4‐oxadiazole (H ₂ DNAO) based Energetic Coordination Polymers (ECPs), namely dipotassium 5,5′‐dinitramino‐3,3′‐azo‐1,3,4‐oxadiazole(K ₂ DNAO), dicesium 5,5′‐dinitramino‐3,3′‐azo‐1,3,4‐oxadiazole(Cs ₂ DNAO) and barium 5,5′‐dinitramino‐3,3′‐azo‐1,3,4‐oxadiazole(BaDNAO) are synthesized for the first time. Synthesized ECPs are thoroughly characterized using infrared spectroscopy (IR), elemental analysis (EA), thermogravimetric analysis and differential scanning calorimetry (TGA‐DSC), field emission scanning electron microscopy (FE‐SEM), and dynamic light scattering (DLS), UV–vis spectroscopy. All ECPs are also confirmed by single‐crystal X‐ray diffraction technique (SC‐XRD). The micro‐ECPs exhibit excellent densities (1.98–2.80 g cm ⁻³ ), insensitivities (IS: 25‐40 J; FS: 240‐360 N), and good thermal stabilities ( T _d : 182–212 °C). K ₂ DNAO and Cs ₂ DNAO show good detonation performance (VOD:7460‐7893 m s ⁻¹ ; DP: 27.5‐30.6 GPa), respectively. To further investigate sub‐micron‐energetics, three sub‐micron ECPs are prepared from their micro counterparts using ultrasonication method, demonstrating significant improvement in thermal stability ( T _d : 194–221 °C) but are highly sensitivity (IS: 2‐15J; FS: 40‐360N). Burning tests of two experimental formulations using micro K ₂ DNAO and Cs ₂ DNAO demonstrate their potential in green pyrotechnic applications. Interestingly, the submicron‐counterparts show remarkable initiating capability. Considering their ease of synthesis, and safety profile, these materials can be effectively transported in their microform and can be rapidly converted into submicron‐form on demand, making them suitable for pyrotechnic applications.