Self-Assembly of Nitrogen-Rich Heterocyclic Compounds with Oxidants for the Development of High-Energy Materials

Abstract

The development of energetic materials with high energy and low sensitivity has attracted immense interests due to their widespread applications in aerospace technology and national defense. In this work, a promising self-assembly strategy was developed to prepare three high-energy materials (1–3) through the introduction of oxidant molecules into the crystal voids of the parent materials. The structures of these new materials were comprehensively examined by infrared spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, and single-crystal X-ray diffraction. In these materials, three unique layer structures with hcb, sql, and interrupted sql topologies were observed, which were formed by the fused-ring-based energetic components. Windows with hexagonal, square, and rectangular structures were observed within these layer structures, which were occupied by H2O2, NO3 –, and ClO4 –, respectively. Oxidant molecules interacted with parent molecules via hydrogen bonds to form crystal structures of these materials. Moreover, the energetic property of these materials was estimated by computing methods. The calculation results revealed that these self-assembly materials exhibit excellent energetic properties. The highest energetic performance was observed for compound 3. The detonation velocity, detonation pressure, and specific impulse values were up to 9339 m·s–1, 42.5 GPa, and 308 s, respectively, which were greater than those of HMX. Furthermore, these materials exhibited good sensitivity, which was closely related to their unique crystal structures. The high performance of these materials indicated that the self-assembly strategy should be a promising method for the development of novel energetic materials.

Ionic Liquid Supported on Magnetic Graphene Oxide as a Highly Efficient and Stable Catalyst for the Synthesis of Triazolopyrimidines

“…Also, [1,2,4]triazolo [1,5-a]pyrimidines, a subtype of bioisosteric purine analogs, have been reported to possess potential antitumor activities, particularly those bearing functional groups at C-5, C-6, or C-7 positions. 46,47 Several synthetic strategies have been described for the preparation of triazolopyrimidine derivatives, most of which are based on a modification of the classical Biginelli reaction. 48,49 Although some of these procedures are efficient, some of them have limiting factors, including long reaction times, side reactions, rigid workup, high-temperature conditions, and nonrecyclable reagents.…”

Energetic host–guest inclusion compounds: an effective design paradigm for high-energy materials

“…Other three host–guest inclusion compounds with 6,8-diamino-7-nitrotetrazolo[1,5- b ]pyridazine (DANTP) and 4,7-diaminopyridazino[4,5- c ]furoxan (DAPF) as hosts and H 2 O 2 , HNO 3 , and HClO 4 as guests were synthesized (DANTP/H 2 O 2 , DAPF/HNO 3 , and DAPF/HClO 4 ). 19 DAPF/HClO 4 exhibits considerably higher specific impulse and is less sensitive than HNIW. A common feature of these compounds is their complicated hydrogen bonding interactions between host and guest molecules.…”

“…18 However, the compound DANTP/H 2 O 2 shows two exothermic peaks in the DTA curve with peak temperatures of 173.1 and 290.1 °C. 19 The first exothermic peak is regarded as the decomposition of H 2 O 2 which is higher than the decomposition temperature of free H 2 O 2 . The extensive intermolecular hydrogen bonds are believed to be the reason why the guests cannot escape from the crystal lattice.…”

Synthesis, thermal behaviors, and energetic properties of asymmetrically substituted tetrazine-based energetic materials

“…For example, trinitrotoluene (TNT), cyclotrimethylene trinitramine (RDX), cyclotetramethylene tetranitramine (HMX), and 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) are represented as the three phases of energy-containing materials, respectively. The reason that hinders the development of energetic materials is the inherent contradiction between energy and safety ( Gao et al, 2020 ; Gettings et al, 2020 ; Du et al, 2021 ; Muravyev et al, 2021 ; Zheng et al, 2021 ). The energy source of traditional nitramine explosives, such as CL-20 and HMX, is the strong redox reaction between the nitro group and the framework structure.…”