Assembly of Tetrazolylfuroxan Organic Salts: Multipurpose Green Energetic Materials with High Enthalpies of Formation and Excellent Detonation Performance

Abstract

A series of highly energetic organic salts comprising a tetrazolylfuroxan anion, explosophoric azido or azo functionalities, and nitrogen‐rich cations were synthesized by simple, efficient, and scalable chemical routes. These energetic materials were fully characterized by IR and multinuclear NMR (1H, 13C, 14N, 15N) spectroscopy, elemental analysis, and differential scanning calorimetry (DSC). Additionally, the structure of an energetic salt consisting of an azidotetrazolylfuroxan anion and a 3,6,7‐triamino‐7H‐[1,2,4]triazolo[4,3‐b][1,2,4]triazolium cation was confirmed by single‐crystal X‐ray diffraction. The synthesized compounds exhibit good experimental densities (1.57–1.71 g cm−3), very high enthalpies of formation (818–1363 kJ mol−1), and, as a result, excellent detonation performance (detonation velocities 7.54–8.26 kms−1 and detonation pressures 23.4–29.3 GPa). Most of the synthesized energetic salts have moderate sensitivity toward impact and friction, which makes them promising candidates for a variety of energetic applications. At the same time, three compounds have impact sensitivity on the primary explosives level (1.5–2.7 J). These results along with high detonation parameters and high nitrogen contents (66.0–70.2 %) indicate that these three compounds may serve as potential environmentally friendly alternatives to lead‐based primary explosives.

Dimethoxycarbonyl Groups Surrounding a Symmetric Diaminobistetrazole Ring: Exploring New Green Energetic Materials

“…In its anionic structure, the tetrazole rings show ad ihedrala ngle N1-N2-N3-N4of 172.6(7)8,a nd the bond length of connecting bond (C2À C2) is 1.480 (17) .T he substituted group is also twisted out of the tetrazole plane (N1-N2-C2-N5 À171.8 (8)8). The sodium center atom is six-coordinated by two oxygen atoms from the dimethoxycarbonyl with NaÀOb ond length of 2.423 (6) and four oxygen atoms from the water molecule with bond lengths www.chemasianj.org ranging from 2.371 (7) to 2.451 (7) (Figure 3b). This sodium salt shows a1 Dc hain structure with alternately assembling units and an adjacent Na···Na distance of 3.176(3) (Na1-Na1).…”

“…Energetic materials play an important role in both military and civilian applications because they are well‐known used as all kinds of explosives, propellants and pyrotechnics . As typical examples of high nitrogen‐containing energetic compounds, the development of tetrazoles and their derivatives has been rapidly benefiting from the efforts of synthetic and theoretical researchers over the past few years . These tetrazoles have characteristics of large number of NN and CN bonds, deriving most of their energy from the high positive heats of formation rather than from the oxidation of the carbon backbone in traditional energetic compounds.…”

“…[1, 2] As typical examples of high nitrogen-containing energetic compounds, [3] the development of tetrazoles and their derivatives has been rapidly benefiting from the efforts of synthetic and theoretical researchers over the past few years. [4][5][6][7][8][9] Theset etrazoles have characteristics of large number of NN and CN bonds, deriving most of their energy from the high positive heats of formation rather than from the oxidationo ft he carbon backbone in traditional energetic compounds. This high nitrogen content also leads to high densities, and the low amount of carbon and hydrogen,w hich allows for ag ood oxygen balance to be achieved more easily.…”

Crystal structure features of nitro derivatives of methylcytizine and their relationship with second-order nonlinear optical susceptibility

“…Another approach is based on the simultaneous analysis of the density of the isolated molecule (d mol ) and a change in this density in going from the free molecule to the crystal (Δ OED ). [51][52][53][54] It is assumed that the molecules interact with each other by overlapping their electron densities. Therefore, the volume of the isolated molecule is larger than that in the crystal.…”

Intermolecular Interactions in Functional Crystalline Materials: From Data to Knowledge

“…Some properties of solids are associated with molecular packing instead of intermolecular interactions. These are such properties as luminescent properties of co-crystals of anticrowns with aromatic molecules and hydrocarbons [72][73][74], electroconductivity of layered donor-acceptor complexes [75,76], optical properties of π-conjugated molecules [77,78], dense packing of high-energetic compounds associated with detonation, and stability properties [59,79]. In this context, it becomes of interest how polytopic molecules or molecules with a lack of limited H-bonding functionalities pack, and which factors govern their packing.…”