Attaining the Utmost Stability and Energy of Carbonyl Azides by the Synergistic Improvement of Conjugation and H-bonding

Carbonyl azides are important precursors to isocyanates and are used as energetic compounds. However, the further development of these compounds is limited by their inherently poor stability. In this study, we present a new family of carbonyl azides, 5-nitro-1H-1,2,4-triazol-3-yl-carbamoyl-azide (NTCA), which was synthesized through in situ oxidation cleavage of amino-tetrazole. Compared with its precursor (nitrocarbamoyl azide, HNCA), X-ray data and quantum calculations indicate that NTCA has much stronger conjugation (dihedral angle decreased from 13.39° to 1.35°) and more H-bonds (increase from 2 to 7 pairs). As a result, NTCA exhibits the highest thermal stability (decomposition temperature of 212 °C) and highest density (1.820 g cm