ABSTRACT
Mono- and dinitro-BN-naphthalenes, i.e., 1-nitro-, 3-nitro-, 1,6-dinitro-, 3,6-dinitro-, and 1,8-dinitro-BNN, were generated in the nitration of 9,10-BN-naphthalene (BNN), a boron-nitrogen (BN) bond-embedded naphthalene, with AcONO2 and NO2BF4 in acetonitrile. The nitrated products were isolated and characterized by NMR, GC-MS, IR, and X-ray single crystallography. The effects of the nitration on the electron density and aromaticity of BNN were evaluated by B-11 NMR analysis and HOMA calculations.
ABSTRACT
Ammonium perchlorate NH4ClO4 (AP) was studied using synchrotron angle-dispersive X-ray powder diffraction (XRPD) and Raman spectroscopy. A diamond-anvil cell was used to compress AP up to 50 GPa at room temperature (RT). Density functional theory (DFT) calculations were performed to provide further insight and comparison to the experimental data. A high-pressure barite-type structure (Phase II) forms at ≈4 GPa and appears stable up to 40 GPa. Refined atomic coordinates for Phase II are provided, and details for the Phase I â II transition mechanics are outlined. Pressure-dependent enthalpies computed for DFT-optimized crystal structures confirm the Phase I â II transition sequence, and the interpolated transition pressure is in excellent agreement with the experiment. Evidence for additional (underlying) structural modifications include a marked decrease in the Phase II b'-axis compressibility starting at 15 GPa and an unambiguous stress relaxation in the normalized stress-strain response at 36 GPa. Above 47 GPa, XRD Bragg peaks begin to decrease in amplitude and broaden. The apparent loss of crystalline long-range order likely signals the onset of amorphization. Three isostructural modifications were discovered within Phase II via Raman spectroscopy. A revised RT isothermal phase diagram is discussed based on the findings of this study.
ABSTRACT
In energetic materials, the crystal density is an important parameter that affects the performance of the material. When making ionic energetic materials, the choice of counter-ion can have detrimental or beneficial effects on the packing, and therefore the density, of the resulting energetic crystal. Presented herein are a series of five ionic energetic crystals, all containing the dianion 5,5'-(3,3'-bi[1,2,4-oxa-diazole]-5,5'-di-yl)bis-(1H-tetra-zol-1-olate), with the following cations: hydrazinium (1) (2N2H5+·C6N12O42-), hydroxyl-ammonium (2) 2NH4O+·C6N12O42- [Pagoria et al.. (2017). Chem. Heterocycl. Compd, 53, 760-778; included for comparison], di-methyl-ammonium (3) (2C2H8N+·C6N12O42-), 5-amino-1H-tetra-zol-4-ium (4) (2CH4N5+·C6N12O42-·4H2O), and amino-guanidinium (5) (2CH7N4+·C6N12O42-). Both the supra-molecular inter-actions and the sterics of the cation play a role in the density of the resulting crystals, which range from 1.544 to 1.873 Mgâ m-1. In 5, the tetra-zolate ring is disordered over two positions [occupancy ratio 0.907â (5):0.093â (5)] due to a 180° rotation in the terminal tetra-zole rings.
ABSTRACT
Recent theoretical studies of 2,6-diamino-3,5-dinitropyrazine-1-oxide (C4H4N6O5 Lawrence Livermore Molecule No. 105, LLM-105) report unreacted high pressure equations of state that include several structural phase transitions, between 8 and 50 GPa, while one published experimental study reports equation of state (EOS) data up to a pressure of 6 GPa with no observed transition. Here we report the results of a synchrotron-based X-ray diffraction study and also ambient temperature isobaric-isothermal atomistic molecular dynamics simulations of LLM-105 up to 20 GPa. We find that the ambient pressure phase remains stable up to 20 GPa; there is no indication of a pressure induced phase transition. We do find a prominent decrease in b-axis compressibility starting at approximately 13 GPa and attribute the stiffening to a critical length where inter-sheet distance becomes similar to the intermolecular distance within individual sheets. The ambient temperature isothermal equation of state was determined through refinements of measured X-ray diffraction patterns. The pressure-volume data were fit using various EOS models to yield bulk moduli with corresponding pressure derivatives. We find very good agreement between the experimental and theoretically derived EOS.
ABSTRACT
Dinitroacetylene and other nitroacetylenes are attractive stoichiometric precursors to high energy-density materials, but suffer from high reactivity and thermal instability. Herein, we report that nitroacetylenes can be dramatically stabilized in the form of their dicobalt hexacarbonyl complexes. In particular, we describe the syntheses and characterization of the first two transition-metal complexes of nitroalkynes, [µ-1-nitro-2-(trimethylsilyl)ethyne-1,2-diyl]bis(tricarbonylcobalt)(Co-Co) and [µ-1-nitroethyne-1,2-diyl]bis(tricarbonylcobalt)(Co-Co). The chemistry of these compounds reveals their potential as reaction partners in [2+2+2] cyclotrimerizations, furnishing nitroindane, nitrotetralin, and trinitrobenzene products. The X-ray crystal structure of 1,3,5-trinitro-2,4,6-tris(trimethylsilyl)benzene presents a distorted, yet planar, aromatic ring.
ABSTRACT
Optical ignition and initiation of energetic materials could thus far be only accomplished through lasers, with specific characteristics of high power, pulse length, wavelength, and a small target area that greatly inhibit their applications. Here, we report that an ignition and an initiation process, further leading to actual detonation, does occur for energetic materials in lax contact with carbon nanotubes that are prone to opto-thermal activity via a conventional flashbulb. Our results show that, for the first time, optical initiation of energetic materials is possible on a large surface area and using ordinary light intensity of several W/cm2. The implication is that energetic materials mixed with optically active nanotubes could be new ideal candidates for safety apparatus, such as the firing of bolts on space shuttle rockets and aircraft exit doors.
