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三维配位聚合物[Cd2(N2H4)2(N3)4]n的研究:晶体结构、热分解机理及爆炸性能

Studies on three-dimensional coordination polymer [Cd2(N2H4)2(N3)4]n: crystal structure, thermal decomposition mechanism and explosive properties.

作者信息

Liu Zhenhua, Zhang Tonglai, Zhang Jianguo, Wang Shaozong

机构信息

State Key Laboratory of Explosion Science and Technology, Beijing Institute of Technology, Beijing 100081, PR China.

出版信息

J Hazard Mater. 2008 Jun 15;154(1-3):832-8. doi: 10.1016/j.jhazmat.2007.10.099. Epub 2007 Nov 4.

Abstract

A 3D coordination polymer of cadmium(II) hydrazine azide, [Cd2(N2H4)2(N3)4]n, was synthesized and characterized by elemental analysis and Fourier transform infrared (FT-IR) spectrum. Its crystal structure was determined by single crystal X-ray diffraction analysis. The crystal belongs to monoclinic, P2(1)/c space group, a=12.555(2)A, b=11.724(2)A, c=7.842(1)A, beta=94.56(2) degrees and Z=4. The crystal contains two crystallographically independent sets of distorted octahedral Cd(II) atoms and dimeric units of Cd2N2, Cd2(NNN)2, Cd2(NN)2 through double micro-1, 1 azide bridges, micro-1, 3 azide bridges and bidentate bridging hydrazine ligands, respectively, and thus generating a 3D network structure. The thermal decomposition mechanism of the complex was studied by using differential scanning calorimetry (DSC), thermogravimetry-derivative thermogravimetry (TG-DTG) and FT-IR techniques. Under nitrogen atmosphere with a heating rate of 10 degrees C/min, the thermal decomposition of the complex contained two intense exothermic decomposition processes in the range of 150-304 degrees C in the DSC curve, and the final decomposed residue at 500 degrees C was Cd. Sensitivity tests revealed that the title complex is very insensitive to external stimuli.

摘要

合成了叠氮化镉(II)肼的三维配位聚合物[Cd2(N2H4)2(N3)4]n,并通过元素分析和傅里叶变换红外(FT-IR)光谱对其进行了表征。通过单晶X射线衍射分析确定了其晶体结构。该晶体属于单斜晶系,P2(1)/c空间群,a = 12.555(2)埃,b = 11.724(2)埃,c = 7.842(1)埃,β = 94.56(2)度,Z = 4。该晶体包含两个晶体学上独立的畸变八面体Cd(II)原子集,以及分别通过双μ-1,1叠氮桥、μ-1,3叠氮桥和双齿桥连肼配体形成的Cd2N2、Cd2(NNN)2、Cd2(NN)2二聚单元,从而形成三维网络结构。采用差示扫描量热法(DSC)、热重-微商热重法(TG-DTG)和FT-IR技术研究了该配合物的热分解机理。在氮气气氛下,升温速率为10℃/min时,配合物的热分解在DSC曲线中150 - 304℃范围内包含两个强烈的放热分解过程,500℃时的最终分解残渣为Cd。灵敏度测试表明,该标题配合物对外部刺激非常不敏感。

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