“…The discovery of new energetic materials (EMs) is one of the growing topics in the field of materials science. − One of the long-term objectives in this field is how to design and synthesize new energetic compounds with high energy, good safety, and high thermal stability. − Recent advances have shown that conjugated skeletons, strong intramolecular hydrogen bonds, and π–π interactions, which are structural features of traditional heat-resistant and insensitive EMs such as 1,3,5-triamino-2,4,6-trinitro-benzene (TATB) and 2,6-diamino-3,5-dinitro-pyrazine-1-oxide (LLM-105), contribute to the low sensitivity and high thermal stability of EMs. − Besides, NN/N–N bonds and nitro groups can increase the density and positive heat of formation (Δ H f ) and lead to the high energy density of EMs such as 1,3,5-trinitro-2,4,6-trinitroaminobenzene (TNTNB), 1,5-diaminotetrazole-4N-oxide (SYX-9), and 2,2′-azo-bis(5-azidotetrazole) . The group of Prof. Ganapathy Vaitheeswaran made some constructive investigations by using calculation methods based on well-known EMs such as ammonium dinitramide (ADN), potassium dinitramide (KDN), 5-aminotetrazole (5-AT), 3,3′-dinitro-5,5′-bis-1,2,4-triazole-1,1′-diolate (DNBTO), 4,4′-bis(nitramino)azofurazan (DNAF), and octanitrocubane (ONC), which also support the above rules. − Bicyclic azolo azines constitute a family of nitrogen-rich conjugated 5/6-fused rings that allow all of the above structural features in one molecule, making them popular building blocks to construct new low-sensitivity and high-energy materials. For example, several reported materials such as 4-amino-3,7,8-trinitropyrazolo-[5,1- c ][1,2,4]triazine ( I , PTX, Figure a), , 4-amino-3,7-dinitrotriazolo-[5,1- c ][1,2,4]triazine ( II , DPX-26 or TTX), , and 6,8-diamino-7-nitrotetrazolo-[1,5- b ]pyridazine ( III ) have shown a good balance between energy and safety.…”