3D Energetic Metal–Organic Frameworks: Synthesis and Properties of High Energy Materials

Abstract

Metal-organic frameworks (MOFs) have attracted great attention because of their intriguing molecular topologies and potential applications in chemical separation, [1] gas storage, [2] drug delivery, [3] catalysis [4] and chemical sensor technology. [5] Particularly, MOFs could also be potential energetic materials because of their high densities and high heats of detonation. For example, Hope-Weeks and co-workers recently reported two hydrazine-perchlorate 1D MOFs [(Ni(NH 2 NH 2 ) 5 (ClO 4 ) 2 ) n (NHP), and (Co(NH 2 NH 2 ) 5 (ClO 4 ) 2 ) n (CHP)] with linear polymeric structures, [6] which were regarded as possibly the most powerful metal-based energetic materials known to date, with heats of detonation comparable with that of hexanitrohexaazaisowutzitane (CL-20; about 1.5 kcal g À1 ).Unfortunately, these coordination polymers were highly sensitive to impact deriving from their low rigidity characteristic of such linear polymeric structures, which makes practical use infeasible. In order to decrease the sensitivities, the same authors also used a hydrazine derivative (hydrazine-carboxylate) as the ligand to construct MOFs with 2D sheet structures [((

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.…”

A green high-initiation-power primary explosive: synthesis, 3D structure and energetic properties of dipotassium 3,4-bis(3-dinitromethylfurazan-4-oxy)furazan

“…15 Further employable cations include the alkali metals cesium or transition metals like copper (DBX-1, Scheme 1 (iv)). 13,[16][17] However, it should be mentioned that copper (II) is also toxic to microorganisms, 18 but to a lesser 5 degree than silver and is therefore not yet desirable. A recently employed idea is the formation of nontoxic metal complexes containing potassium instead of toxic heavy metals.…”

Synthesis and Characterization of Tetrahedral Zinc(II) Complexes with 3, 6,7‐Triamino‐7H‐[1, 2,4]triazolo[4, 3‐b][1, 2,4]triazole as Nitrogen‐Rich Ligand

“…[10] Prominent examples are 5-(1-methylhydrazinyl)-1H-tetrazole, [11] 3-hydrazino-4-amino-1,2,4-triazole, [12] 5,5Ј-bis(1H-tetrazolyl)amine, [13] and 3-amino-6-(3,5-dimethylpyrazole)-tetrazine, [14] which are illustrated in Figure 1. Figure 2).…”