A convenient synthetic route toward new copper(II) chlorate complexes with potential use in modern advanced ignition or initiation systems is described. Obtained compounds were not only accurately characterized (XRD, IR, UV/Vis EA and DTA) but also investigated for their energetic character (sensitivities, initiation capability and laser ignition). The copper 4-aminotriazolyl chlorate complex showed excellent initiation of PETN, while also being thermally stable and safe to handle. Solid-state UV-Vis measurements were performed to get a possible insight toward the laser initiation mechanism. In contrast to expectations, the presented copper(II) chlorate energetic coordination compounds show manageable sensitivities that can be tamed or boosted by the appropriate choice of nitrogen-rich ligands.

Numerous energetic coordination complexes (MnII, FeII, CoII, NiII, CuII, ZnII, and AgI) using 1-methyl-tetrazole as the ligand were synthesized and tuned by different counteranions (e.g. NO3−, ClO4−, picrate, and styphnate). They show great potential for mechanical or optical initiation systems.

This comprehensive study features the synthesis, characterization and evaluation of new energetic coordination compounds (ECC) based on two of the most powerful neutral tetrazoles, which have great potential as lead-free primary explosives.

Energetic coordination compounds (ECC) based on 3d or 4d transition metals show promising characteristics to be used as potential replacements for highly toxic leadcontaining primary explosives. Herein we report the synthesis of 12 new ECC based on 1-azidoethyl-5H-tetrazole (AET) or 1-ethyl-5H-tetrazole (1-ETZ) as nitrogen-rich ligandsa s well as variousc entral metals (Cu 2 + ,F e 2 + ,Z n 2 + ,A g + )a nd anions such as perchlorate and nitrate. The influence of the increased endothermicity by adding an additional azide group was studied by comparing analogous ECC based on AET and 1-ETZ. Furthermore, the compounds were extensively analyzed by XRD, IR, EA, solid-state UV/Vis,a nd DTAa s well as their sensitivities toward impactand friction were determined with BAM standard techniques, together with their sensitivity against electrostatic discharge. The sensitivities were compared with the one toward ball drop impact measurements. Classicali nitiation tests (nitropenta filled detonators) and ignitionbylaser irradiation highly prove the potential use of the most promising compounds in lead-freei nitiation systems.[a] M.

A concept for stabilizing highly sensitive and explosive copper(II) azide with 1‐N‐substituted tetrazoles is described. It was possible to stabilize the system by the use of highly endothermic, nitrogen‐rich ligands. The sensitivities of the resulting energetic copper coordination compounds can be tuned further by variation of the alkyl chain of the ligands and by phlegmatization of the complexes with classical additives during the synthesis. It is demonstrated, using the compound based on 1‐methyl‐5H‐tetrazole ([Cu(N3)2(MTZ)], 1) that this class of complexes can be applied as a potential replacement for both lead azide (LA) and lead styphnate (LS). The complex was extensively investigated according to its chemical (elemental analysis, single‐crystal and powder X‐ray diffraction, IR spectroscopy, scanning electron microscopy) and physico‐chemical properties (differential thermal analysis, sensitivities towards impact, friction, and electrostatic discharge) compared to pure copper(II) azide.

The synthesis of di(1H-tetrazol-5-yl)methane (1, 5-DTM), starting from commercially available sodium azide and malononitrile, is described. This tetrazole was characterized and investigated for use as a neutral nitrogen-rich ligand in various energetic transition metal complexes: ([CuCl(5-DTM)]·2HO (2), [Co(HO)(5-DTM)]Cl (3), [Ni(HO)(5-DTM)]Cl (4), [Co(HO)(5-DTM)](NO) (6), [Ni(HO)(5-DTM)](NO) (7), [Zn(HO)(5-DTM)](NO) (8), {[Cu(SO)(5-DTM)(HO)(5-DTM)]·2HO} (9), [Cu(HO)(5-DTM)](NO) (11), [Cu(NO)(5-DTM)]·2HO (12), [Cu(NO)(5-DTM)] (13), [Cu(HO)(5-DTM)](ClO) (14), and [Cu(ClO)(5-DTM)] (15). Obtained coordination compounds were characterized using single crystal X-ray diffraction (except for 7 and 13), IR spectroscopy, elemental analysis, and differential thermal analysis. The sensitivities to external stimuli (impact, friction, electrostatic discharge) were determined. Complexes 12 and 13 were tested for their ignitability by laser irradiation.

1,1'-Dinitramino-5,5'-bitetrazole and 1,1'-dinitramino-5,5'-azobitetrazole were synthesized for the first time. The neutral compounds are extremely sensitive and powerful explosives. Selected nitrogen-rich salts were prepared to adjust sensitivity and performance values. The compounds were characterized by low-temperature X-ray diffraction, IR and Raman spectroscopy, multinuclear NMR spectroscopy, elemental analysis, and DTA/DSC. Calculated energetic performances using the EXPLO5 code based on calculated (CBS-4M) heats of formation and X-ray densities support the high performances of the 1,1'-dinitramino-5,5'-bitetrazoles as energetic materials. The sensitivities toward impact, friction, and electrostatic discharge were also explored. Most of the compounds show sensitivities in the range of primary explosives and should only be handled with great care!

The preparation of 5-(1-methylhydrazinyl)-1H-tetrazole monohydrate (1⋅H2O) and various copper(II) complexes with perchlorate (2 and 3), nitrate (4, 5, and 6), dinitramide (7), and chloride (8) is described. The coordination compounds (monomers, dimers, and polymers) were characterized through infrared spectroscopy and elemental analysis. Further, the structures of 2 and 4-8 were determined by single-crystal X-ray diffraction. Compound 1 can act as a bidentate ligand in its neutral form (HMHT) and as a μ2- or μ3-bridging ligand in its deprotonated form (MHT). The energetic properties of the synthesized complexes, such as their sensitivities toward impact and friction, were determined, and laser ignition tests were performed. New information about the laser initiation process and the role of the anion in the initiation criterion was obtained. The perchlorate complexes 2 (T(decomp)=217 °C) and 3 (T(decomp)=206 °C) are potential primary explosives.