Cocrystallization of Photosensitive Energetic Copper(II) Perchlorate Complexes with the Nitrogen-rich Ligand 1,2-Di(1H-tetrazol-5-yl)ethane

Abstract

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.

Cooperative enhancement of the nonlinear optical response in conjugated energetic materials: A TD-DFT study

“…Recent efforts have focused on photoactive energetic materials with absorption within the range of conventional lasers. [10][11][12][13][14][15][16][17][18][19][20][21][22][23] Introducing a fiber optic cable for direct optical initiation eliminates sensitivity to electrical insults, while replacing primary explosives with less sensitive secondary explosives reduces sensitivity to mechanical insults. A class of energetic materials that exhibit the optical, electrical, and mechanical properties suitable for this application are conjugated energetic molecules (CEMs).…”

Nitrogen-Rich Energetic Metal-Organic Framework: Synthesis, Structure, Properties, and Thermal Behaviors of Pb(II) Complex Based on N,N-Bis(1H-tetrazole-5-yl)-Amine

“…The sensitivities of these 3D MOFs are significantly lower than those of reported energetic coordination polymers, such as 1D (CHP, IS = 0.5 J) and 2D (ZnHHP, IS = 2.5 J; CHHP, IS = 0.8 J) MOFs. An increasing number of investigations on E-MOFs as new-generation high explosives were reported by Chen et al [32,33,36,38,39,40,42,44,45,50,51], Pang et al [28,48,52], Shreeve et al [49,53], and so on [41,47,54,55,56] because of the advantages of 3D MOFs.…”

The dependence of the critical energy density and hot-spot temperature on the radius of metal nanoparticles in PETN

“…Optical detonators based on silver azide [3,4] have minimum thresholds value when initiated with laser pulse, but they are also sensitive to other types of impact (heat, electric spark, etc.). To create selectively sensitive materials to laser radiation, one introduces light-absorbing nanoparticles [5] or the synthesis of new compound with absorption bands matching the wavelength of the radiation sources to the existing transparent explosives [6][7][8]. The minimum initiation energy density of explosive decomposition of the regular blasting explosives (PETN and RDX) with additives of aluminum [2,9,10], nickel [10,11] and other metals nanoparticles is of the order of 1 J/cm 2 , which is more than hundred times less than for pure pressed tablets of this explosives.…”