Polynitro‐Functionalized Dipyrazolo‐1,3,5‐triazinanes: Energetic Polycyclization toward High Density and Excellent Molecular Stability

A new fused N‐heterocyclic framework, dipyrazolo‐1,3,5‐triazinane, was synthesized and the physiochemical properties of its derivatives were investigated to evaluate the integrated energetic performance. In contrast to 1,3,5‐trinitro‐1,3,5‐triazinane (RDX) featuring a distorted chair confirmation, polynitro‐functionalized dipyrazolo‐1,3,5‐triazinanes have nearly planar backbones, thereby enhancing the density and thermal stability. Among these new energetic tricyclic compounds, 5 a and 12 show favorable crystal densities of 1.937 g cm⁻³ and 1.990 g cm⁻³ at 150 K, respectively, which rank highest in triazinane‐based energetic compounds. Additionally, this synthetic approach was carried out to form seven‐membered and eight‐membered rings, giving rise to tetranitro dipyrazolo‐1,3,5‐triazepane ( 5 b ) and tetranitro dipyrazolo‐1,3,5‐triazocane ( 5 c ), respectively.