The reaction of [N(2)H(5)](+)(2)[SO(4)](2-) with barium 5,5'-azotetrazolate gave new high-energy-density materials (HEDM) based on the 5,5'-azotetrazolate dianion. The dihydrazinium salt of [N(4)C-N=N-CN(4)](2-) 1, its dihydrate 2, and its dihydrazinate 3 were prepared in high yield. Synthesis in water afforded yellow needles of [N(2)H(5)](2)(+)[N(4)C-N=N-CN(4)](2-).2H(2)O (2): monoclinic, P2/c, a = 8.958(2) A, b = 3.6596(7) A, c = 16.200(3) A, beta = 96.834(3) degrees, V = 527.3(2) A(3), Z = 2; synthesis in anhydrous hydrazine gave yellow [N(2)H(5)](2)(+)[N(4)C-N=N-CN(4)](2-).2N(2)H(4) (3): triclinic, P1, a = 4.6208(6) A, b = 8.585(1) A, c = 9.271(1) A, alpha = 108.486(2) degrees, beta = 95.290(2) degrees, gamma = 102.991(2) degrees, V = 334.51(8) A(3), Z = 1. The compounds were characterized by elemental analysis and vibrational (IR, Raman) and multinuclear NMR spectroscopy ((1)H, (13)C, (14)N, (15)N). The new compounds represent new high-nitrogen HEDMs with one of the highest nitrogen contents reported to date ([N(2)H(5)](+)(2)[N(4)C-N=N-CN(4)](2-) 85.2%; [N(2)H(5)](+)(2)[N(4)C-N=N-CN(4)](2-).2H(2)O 73.3%; [N(2)H(5)](+)(2)[N(4)C-N=N-CN(4)](2-).2N(2)H(4) 85.7%). The standard heat of formation of the solvate-free compound 1 was computed at the MP2(FULL)/6-311+G(d,p) level of theory to be DeltaH degrees (f) = 264 kcal mol(-1), which translates to 1147 kcal kg(-1) and is one of the highest ever reported. The compounds are stable at room temperature, almost insensitive to friction and impact, but detonate violently when the explosion is initiated, e.g., by rapid heating over the decomposition temperature or by using an initiator.

Glycidyl azide-r-(3,3-bis(azidomethyl)oxetane) copolymers were synthesized by cationic copolymerization of epichlorohydrin and 3,3-bis(bromomethyl)oxetane, using butane-1,4-diol as initiator and boron trifluoride etherate as catalyst, followed by azidation of the halogenated copolymer. The main objective of this work is the preparation of an amorphous polymer with energetic content higher than that of the well known glycidyl azide homopolymer. The effect of experimental conditions, like i.e. the rate of monomer feeding, on the final molecular weight and functionality of the copolymer has also been investigated. The obtained copolymers were extensively characterized to determine their composition and thermal stability. The heat of reaction for the polymerisation of the halogenated key precursors has also been measured.

Salts of the 5,5'-azotetrazolate dianion with several different hydrazinium cations were pre pared. The compounds were characterized by elemental analysis, vibrational spectroscopy (IR, Raman) and multinuclear NMR spectroscopy ( 'H, i3C, l4 N). The crystal structures of the di-terf-butylhydrazinium, the ethylenedihydrazinium, the diguanidinium and the bis-triaminoguanidinium azotetrazolate were determined. The thermal, shock and friction sensitivities of all compounds were investigated and their explosion products were analysed. For the 5,5'-azotetrazolate dianion the structure was calculated with density functional theory (B3-LYP). An NBO analysis was performed for the 5,5'-azotetrazolate dianion in order to understand the charge distribution of the dianion. Results and Discussion

Solutions of N, N′‐azobistetrazolate salts in anhydrous hydrazine were reduced to salts of N, N′‐bistetrazolatohydrazine. Several salts of this highly energetic, nitrogen rich anion were prepared this way and characterized by elemental analysis, vibrational (IR, Raman) and multinuclear NMR spectroscopy (1H, 13C, 14N). The crystal structure of the barium and hydrazinium salt were determined.

No abstract