Metal complexes of the pentazole anion exhibit multiple coordination modes, through ionic, covalent and hydrogen-bonding interactions, and good thermal stability with onset decomposition temperatures greater than 100 °C. Polynitrogen compounds can decompose to N2 with an extraordinarily large energy release, which makes them promising candidate materials for explosives but difficult to produce in a stable form. Compounds containing five-membered all-nitrogen rings have attracted particular interest in the search for a stable polynitrogen molecule. Yuangang Xu et al. report five metal complexes containing the pentazole anion, cyclo--N5−, four of which exhibit good thermal stability and a range of different bonding interactions for stabilization. Given their energetic properties and stability, and the adaptability of the cyclo-N5− species in terms of its bonding interactions, these complexes might lead to the development of a new class of high-energy-density materials and of other unusual polynitrogen complexes. Singly or doubly bonded polynitrogen compounds can decompose to dinitrogen (N2) with an extremely large energy release. This makes them attractive as potential explosives or propellants1,2,3, but also challenging to produce in a stable form. Polynitrogen materials containing nitrogen as the only element exist in the form of high-pressure polymeric phases4,5,6, but under ambient conditions even metastability is realized only in the presence of other elements that provide stabilization. An early example is the molecule phenylpentazole, with a five-membered all-nitrogen ring, which was first reported in the 1900s7 and characterized in the 1950s8,9. Salts containing the azide anion (N3−)10,11,12 or pentazenium cation (N5+)13 are also known, with compounds containing the pentazole anion, cyclo-N5−, a more recent addition14,15,16. Very recently, a bulk material containing this species was reported17 and then used to prepare the first example of a solid-state metal–N5 complex18. Here we report the synthesis and characterization of five metal pentazolate hydrate complexes [Na(H2O)(N5)]·2H2O, [M(H2O)4(N5)2]·4H2O (M = Mn, Fe and Co) and [Mg(H2O)6(N5)2]·4H2O that, with the exception of the Co complex, exhibit good thermal stability with onset decomposition temperatures greater than 100 °C. For this series we find that the N5− ion can coordinate to the metal cation through either ionic or covalent interactions, and is stabilized through hydrogen-bonding interactions with water. Given their energetic properties and stability, pentazole–metal complexes might potentially serve as a new class of high-energy density materials19 or enable the development of such materials containing only nitrogen20,21,22,23. We also anticipate that the adaptability of the N5− ion in terms of its bonding interactions will enable the exploration of inorganic nitrogen analogues of metallocenes24 and other unusual polynitrogen complexes.

A series of energetic metal pentazolate hydrates

Finding new high-energy-density materials with desired properties has been intensely-pursued in recent decades. However, the contradictory relationship between high energy and low mechanical sensitivity makes the innovation of insensitive high-energy-density materials an enormous challenge. Here, we show how a materials genome approach can be used to accelerate the discovery of new insensitive high-energy explosives by identification of “genetic” features, rapid molecular design, and screening, as well as experimental synthesis of a target molecule, 2,4,6-triamino-5-nitropyrimidine-1,3-dioxide. This as-synthesized energetic compound exhibits a graphite-like layered crystal structure with a high measured density of 1.95 g cm−3, high thermal decomposition temperature of 284 °C, high detonation velocity of 9169 m s−1, and extremely low mechanical sensitivities (impact sensitivity, >60 J and friction sensitivity, >360 N). Besides the considered system of six-member aromatic and hetero-aromatic rings, this materials genome approach can also be applicable to the development of new high-performing energetic materials. The synthesis of explosive materials that are stable, highly dense, and have low sensitivity to external stimuli is a challenge. Here, the authors use a genomic approach to accelerate the discovery of insensitive high explosive molecules with good detonation and low sensitivity properties.

/pdf/accelerating-the-discovery-of-insensitive-high-energy-1lubafpy2f.pdf

Accelerating the discovery of insensitive high-energy-density materials by a materials genome approach

High-energy density materials represent a significant class of advanced materials and have been the focus of energetic materials community. The main challenge in this field is to design and synthesize energetic compounds with a highest possible density and a maximum possible chemical stability. Here we show an energetic compound, [2,2′-bi(1,3,4-oxadiazole)]-5,5′-dinitramide, is synthesized through a two-step reaction from commercially available reagents. It exhibits a surprisingly high density (1.99 g cm−3 at 298 K), poor solubility in water and most organic solvents, decent thermal stability, a positive heat of formation and excellent detonation properties. The solid-state structural features of the synthesized compound are also investigated via X-ray diffraction and several theoretical techniques. The energetic and sensitivity properties of the explosive compound are similar to those of 2, 4, 6, 8, 10, 12-(hexanitrohexaaza)cyclododecane (CL-20), and the developed compound shows a great promise for potential applications as a high-energy density material. High energy density materials are of interest, but density is the limiting factor for many organic compounds. Here the authors show the formation of a high density energetic compound from a two-step reaction between commercially available compounds that exhibit good heat thermal stability and detonation properties.

/pdf/a-promising-high-energy-density-material-onkryg648l.pdf

A promising high-energy-density material

The coupling of two or more molecules of dinitrogen (N2) occurs naturally under the radiative conditions present in the ionosphere and may be achieved synthetically under ultrahigh pressure or plasma conditions. However, the comparatively low N-N single-bond enthalpy generally renders the catenation of the strongly triple-bonded N2 diatomic unfavorable and the decomposition of nitrogen chains a common reaction motif. Here, we report the surprising organoboron-mediated catenation of two N2 molecules under near-ambient conditions to form a complex in which a [N4]2- chain bridges two boron centers. The reaction entails reductive coupling of two hypovalent-boron-bound N2 units in a single step. Both this complex and a derivative protonated at both ends of the chain were characterized crystallographically.

The reductive coupling of dinitrogen.

Poly-nitrogen compounds have been considered as potential high energy density materials for a long time due to the large number of energetic N-N or N=N bonds. In most cases high nitrogen content an ...

/pdf/fe-n-system-at-high-pressure-reveals-a-compound-featuring-5gn1fv40ui.pdf

Fe-N System at High Pressure Reveals a Compound Featuring Polymeric Nitrogen Chains

The flip side of the robust stability of N2 is the instability of any larger molecules composed exclusively of nitrogen. These molecules nonetheless remain enticing targets for explosive and propellant applications. Zhang et al. successfully prepared the pentazolate ion, a negatively charged ring of five nitrogens, by oxidative cleavage of a C–N bond in an aryl-substituted precursor (see the Perspective by Christe). The molecule was stabilized and isolated in the solid state as a hydrated ammonium chloride salt. Spectroscopic and crystallographic characterization confirmed the ring's planar geometry.

Science , this issue p. [374][1]; see also p. [351][2]

 [1]: /lookup/doi/10.1126/science.aah3840
 [2]: /lookup/doi/10.1126/science.aal5057

http://science.sciencemag.org/content/sci/355/6323/374.full.pdf

Synthesis and characterization of the pentazolate anion cyclo-N5ˉ in (N5)6(H3O)3(NH4)4Cl

The reactions of (N5)6(H3O)3(NH4)4Cl with Co(NO3)2⋅6 H2O at room temperature yielded Co(N5)2(H2O)4⋅4 H2O as an air-stable orange metal complex. The structure, as determined by single-crystal X-ray diffraction, has two planar cyclo-N5− rings and four bound water molecules symmetrically positioned around the central metal ion. Thermal analysis demonstrated the explosive properties of the material.

Chuanming Yu

Papers

Synthesis and characterization of the pentazolate anion cyclo-N5ˉ in (N5)6(H3O)3(NH4)4Cl

A Symmetric Co(N5)2(H2O)4⋅4 H2O High-Nitrogen Compound Formed by Cobalt(II) Cation Trapping of a Cyclo-N5− Anion