The most comprehensive approach to analyze and characterize energetic materials is suggested and applied to enable rational, rigorous design of novel materials and targeted improvements of existing materials to achieve desired properties. We report synthesis, characterization of the structure and sensitivity, and modeling of thermal and electronic stability of the energetic, heterocyclic compound, 3,4-bis(4-nitro-1,2,5-oxadiazol-3-yl)-1,2,5-oxadiazole-2-oxide (BNFF). The proposed novel, relatively simple synthesis of BNFF in excellent yields allows for an efficient scale up. Performing careful characterization indicates that these materials offer an unusual combination of properties and exhibit a relatively high energy density, high and controllable stability against decomposition, low melting temperature, and low sensitivity to initiation of detonation. First-principles calculations of activation barriers and reaction rate constants reveal the decomposition scenarios that govern the thermal stability and chemical behavior of BNFF, which appreciably differ from conventional nitro compounds. Details of the electronic structure and calculated electronic properties suggest that BNFF is an excellent candidate energetic material on its own and an attractive ingredient of modern energetic formulations to improve their stability and enable highly controllable chemical decomposition.

A methodology to design novel energetic materials by means of a holistic approach that links synthesis, experimental characterization, quantum-chemical modeling, and statistical empirical evaluation is proposed. An analysis of the revealed structure–property–function correlations in the LLM compound series (oxadiazole-based heterocyclic energetics), BNFF, BNFF-1, LLM-172, LLM-191, and LLM-192, led us to predict, obtain, and characterize a new member in the materials family, LLM-200, which exhibits attractive energetic characteristics compared to known conventional high energy density materials. While the applied strategy convincingly demonstrated feasibility of the end-to-end design of high energy density materials, there are certain limitations in parallel improvements of sensitivity and performance within a single compound.

A description of the various approaches to the synthesis of the insensitive energetic compound, 2,6-diamino-3,5-dinitropyrazine-1-oxide (LLM-105), developed at LLNL over the past 20 years will be described.

The title compound 3-(4-amino-1,2,5-oxadiazol-3-yl)-4-(4-nitro-1,2,5oxadiazol-3-yl)-1,2,5-oxadiazole (ANFF-1) was synthesized by: (1) by reaction of 3,4-bis(4-nitro-1,2,5-oxadiazol-3-yl)-1,2,5-oxadiazole (BNFF-1) with gaseous ammonia in toluene and (2) by partial oxidation of 3,4-bis(4-amino-1,2,5-oxadiazol-3-yl)-1,2,5oxadiazole (BAFF-1) with 35% H 2 O 2 in concentrated H 2 SO 4 .

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.