Taming Dinitramide Anions within an Energetic Metal–Organic Framework: A New Strategy for Synthesis and Tunable Properties of High Energy Materials

Abstract

Energetic polynitro anions, such as dinitramide ion [N­(NO2)2 –], have attracted significant interest in the field of energetic materials due to their high densities and rich oxygen contents; however, most of them usually suffer from low stability. Conveniently stabilizing energetic polynitro anions to develop new high energy materials as well as tuning their energetic properties still represent significant challenges. To address these challenges, we herein propose a novel strategy that energetic polynitro anions are encapsulated within energetic cationic metal–organic frameworks (MOFs). We present N­(NO2)2 – encapsulated within a three-dimensional (3D) energetic cationic MOF through simple anion exchange. The resultant inclusion complex exhibits a remarkable thermal stability with the onset decomposition temperature of 221 °C, which is, to our knowledge, the highest value known for all dinitramide-based compounds. In addition, it possesses good energetic properties, which can be conveniently tuned by changing the mole ratio of the starting materials. The encapsulated anion can also be released in a controlled fashion without disrupting the framework. This work may shed new insights into the stabilization, storage, and release of labile energetic anions under ambient conditions, while providing a simple and convenient approach for the preparation of new energetic MOFs and the modulation of their energetic properties.

Methylsemicarbazide as a Ligand in Late 3d Transition Metal Complexes

“…Various combinations have been described in the literature . Highly energetic and sensitive complexes are formed by the combination of hydrazine derivatives (hydrazine, monomethylhydrazine, dimethylhydrazine, semicarbazide (SC), carbohydrazide (CHZ) but also N ‐amino‐azoles) as the ligand with nitrate or perchlorate transition metal salts . One of the most prominent ECC of this type is NHN (nickel hydrazine nitrate) which has also successfully been tested in detonators but contains very toxic nickel(II) …”

Molecular perovskite high-energetic materials

“…Loading more nitro groups and higher structural tension into a single molecule does improve explosive performance, but usually leads to complicated and not cost-effective synthetic procedures. By a trade-off of detonation performance and cost, HMX is regarded as the best military high-energetic explosives nowadays [7], although it is neither the most powerful one nor the cheapest one.Parallel to the intensive studies on molecule engineering on the backbone of nitrogen-rich organic energetic molecules [8,9], the exploration of advanced energetic materials extends to the crystal engineering on their energetic co-crystals [10-13], energetic salts [14][15][16][17][18][19][20], as well as coordination polymers or metal-organic frameworks [21][22][23][24][25][26][27]. The essential strategy is to control the intermolecular packing/linkage of the energetic organic fuel and oxidizer components in crystals by non-covalent interactions to modify/enhance the explosive performance and/or to reduce the sensitivity to a practicable level.…”

Nitrogen-Rich Energetic Metal-Organic Framework: Synthesis, Structure, Properties, and Thermal Behaviors of Pb(II) Complex Based on N,N-Bis(1H-tetrazole-5-yl)-Amine

“…Many investigators have recently demonstrated the possibility of using nitrogen-rich MOFs as high explosives [25,26,27,28,29,30,31,32,33,34,35,36,37,38,39,40,41,42,43,44,45,46,47,48]. MOFs consist of metal ions (Pb 2+ , Ag + , etc.…”