Synthesis And Properties Of Oxygen-rich Poly-nitrogen Triazolate And Tetrazolate-metal Complexes

In recent years, Nitrogen-rich heteroaromatic (such as triazolate and tetrazolate) metalcomplexes have emerged as a new class of Metal-Organic materials with intriguingmolecular structures, rich electronic effect, unsaturated metal sites, efficient active points.These properties makes metal coordination compounds for potential applications inmagnetism, optics, gas adsorption. At the same time, theses metal complexes could also beenergetic materials because of their high density, high heat resistance, high heats ofdetonation, environmentally benign nitrogen gas.Despite these advances, current energetic coordination compounds are only limited tobe a or multiple nitrogen heterocyclic structure with low oxygen content. A series ofOxygen-rich poly-nitrogen heterocyclic metal complexes have been designed andsynthesized for the first time in the paper; Their structures, properties and the syntheticmethods of ligands have also been investigated.Firstly, the synthetic methods of three oxygen-rich more nitrogen heterocyclic ligandshave been optimized. The paper preliminary explored the best of the reaction conditionsand simplify the post-processing to3,3’-dinitro-5,5’-azo-1H-1,2,4-triazole(DNAT), whichcontribute to make the yield as high as70%above; and the paper also simplify thereaction conditions of5,5’-bistetrazole-1,1’-diolate(Kx-50) to improve the experimentalefficiency and cost savings.Secondly,3-chloro-3’-nitro-5,5’-azo-1H-1,2,4-triazole obtained unexpectedly werecharacterized by X-ray single crystal diffraction. It belong to orthorhombic system with thedensity of1.728gcm-3. Owning to conducting easily nucleophilic substitution reaction,reduction reaction, It could have potential applications in synthesizing excellent propertiesof energetic compounds.Finally，Through solvothermal synthesis in chapter3, five novel energetic metalorganic complexes [Zn[(DNBT)2.(CH3OH)].2(CH3OH)],[Zn[(NH3)2.(OH)2].(DNBT)],[Cu[(Kx-50)2].(NO3)2],[Zn[(Kx-50)2].(NO3)2],[Ag[(Kx-50)].(NO3)2] which use enrichedoxygen poly-nitrogenheterocycles as ligands have been designed and synthesized for thefiret time. These complexes were characterized by elemental analysis, IR and X-ray singlecrystal diffraction. In chapter4, Thermal decomposition process and the sensitivity of the two Metal-DNBT complexes were investigated. At the same time, the heat of detonation,the detonation press and the detonation velocity of3-chloro-3’-nitro-5,5’-azo-1H-1,2,4-triaz-ole were estimated with code DMO13and Kamlet-Jacobs formula. Its energetic propertiesis comparable to TNT.