3-Amino-1-nitroguanidine (ANQ, 2) was synthesized via hydrazinolysis of nitroguanidine. By dissolving 2 in solutions containing transition metal salts, several complexes M(2+)(ANQ)2X2(H2O)y with M(2+) = Co, Ni, Cu, Zn as well as M(ANQ)2X(H2O)y with M = Ag could be isolated. In these cases, nitrate as well as perchlorate and chloride served as the respective anions X. Additionally, the ANQ complexes of Co, Ni, and Ag with dinitramide as the anion were synthesized from ANQ and silver dinitramide and by reacting the cobalt and nickel ANQ perchlorate complexes with ammonium dinitramide. The crystal structures of all described complexes were determined by low temperature single-crystal X-ray diffraction. Additionally, they were characterized using IR spectroscopy and elemental analysis. The decomposition temperatures were determined by differential scanning calorimetry and the sensitivities toward impact and friction were assessed using a BAM drophammer and a BAM friction tester (BAM = Bundesanstalt für Materialforschung und -prüfung). Additionally, the sensitivity toward electrostatic discharge was determined on a small-scale ESD device. The potential use of the nitrate, dinitramide and perchlorate containing species as primary explosives was investigated in a laser ignition test.

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.

Two recently introduced concepts in the design of new energetic materials, namely complexation and cocrystallization, have been applied in the synthesis and characterization of the energetic copper(II) compound "[Cu(dt-5-e)2(H2O)](ClO4)2," which consists of two different complex cations and can be described as a model energetic ionic cocrystal. The presence of both the N-rich 1,2-di(1H-tetrazol-5-yl)ethane ligand and oxidizing perchlorate counterion results in a new type of energetic material. The ionic complex cocrystal consists of a mononuclear and a trinuclear complex unit. It can be obtained by precipitation from perchloric acid or by dehydration of the related mononuclear coordination compound [Cu(dt-5-e)2(H2O)2](ClO4)2·2H2O at 70 °C in the solid state. The transformation starting at 60 °C was monitored by X-ray powder diffraction and thermal analysis. The energetic ionic cocrystal was shown to be a new primary explosive suitable for laser ignition. The different coordination spheres within the ionic cocrystal (octahedral and square pyramidal) were shown by UV/vis/NIR spectroscopy to result in excellent light absorption.

The synthesis and characterization (including NMR spectroscopy, elemental analysis, X-ray diffraction, infrared spectroscopy and sensitivity measurements) of 1,2-bis[5-(1-methylhydrazinyl)tetrazol-1-yl]ethane (1) and its corresponding metal [Cu 2+ (2), Co 2+ (3), Ni 2+ (4)] complexes is presented. The crystal structure of the copper(II) complex was determined and infrared spectra of all three coordination com- [a]493 pounds were recorded. Furthermore, the behaviour of the metal(II) complexes towards single-pulsed laser irradiation was investigated and it was shown that all three perchlorate complexes detonated after initiation by monopulsed laser light. The initiation mechanism seems to be of thermal nature.

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