After carefully analyzing the Kamlet–Jacobs (K–J) equations and the structural traits of well-known explosives, hexahydro-1,3,5-trinitro-1,3,5-triazin (RDX), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), and hexanitrohexaazaisowurtizitane (CL-20), diverse nitramine explosives including linear (Models IA n , IB n , and IC n ), cyclic (Model II n ), and caged (Models IIIA n and IIIB n ) molecules were designed by incorporating various number ( n ) of −CH 2 NNO 2 – structural unit and studied using the B3LYP/6-31G* and B3PW91/6-31G** methods of the density functional theory. Computational results show that all of the energetic parameters, that is, density (ρ), detonation velocity ( D ), and detonation pressure ( P ), follow the order of IIIB n > IIIA n > II n > IA n > IB n > IC n . With the increasing n , the D and P of linear nitramines eventually keep stable. This clearly indicates that elongating the chain length (e.g., polymerization) brings little or even negative benefit in boosting the explosive properties. The oxygen balance and the K–J equation parameter ϕ both have a significant influence on the detonation properties. Caged compound IIIA2 has not only comparable energetic properties but also better sensitivity and thermal stability than CL-20.

In our effort to seek for the "green" energetic coordination polymers (CPs), a versatile and multifunctional 1-amino-tetrazol-5-one ligand was synthesized and its complexes with a series of alkaline and earth alkaline metals were prepared and comprehensively characterized. A broad range of differently shaped 1D, 2D, and 3D supramolecular structures for the prepared energetic compounds were found, where each metal was bound in a specific and characteristic fashion. All prepared CPs show very good thermostability, with decomposition temperatures above 236 °C and remarkable insensitivity to mechanical impact and friction (impact sensitivity > 40 J, friction sensitivity > 360 N). In terms of detonation performance, our CPs were calculated to have detonation velocities in the range of 6.8−8.1 km•s −1 and detonation pressures in the range of 16.5−24.5 GPa. Upon their combustion, new materials show a range of characteristic flame colors (from yellow to blue), making these compounds as promising components for various "green" pyrotechnic formulations.

Three DNP (3,4-dinitropyrazole) salts and one DNP cocrystal were synthesized and characterized by IR, elemental analysis, and single-crystal X-ray diffraction. DSC analysis shows that hydrazine hydrate (HH), ethanediamine (ED), aminoguanidine (AG), and urea (U) all make DNP prone to decomposition, demonstrating that salt formation and cocrystallization are two strategies to modulate the thermal stability and the coformers play a vital role in the performance of the target products. Hirshfeld surfaces suggest that O•••H close contacts make the greatest contribution to the stabilization of I− IV. Electrostatic potential and pK a values give a reasonable explanation that DNP forms salts I−III with HH, ED, and AG, while it forms cocrystal IV with U. The hydrogen-bonding interactions were evaluated by the quantum theory of atoms-in-molecules (AIM) and the independent gradient model (IGM), further revealing that DNP and U prefer to form a cocrystal, rather than a salt or as the individual compounds. The systematic experimental and theoretical work gives a clear comparison of the salt and cocrystal formation processes and explains their origins on the atomic scale, which can prompt the development of the design and synthesis of new salts and cocrystals.

Prediction of miscibility and mechanical properties of GAP/DIANP blends.