High-Density Energetic Metal-Organic Frameworks Based on the 5,5'-Dinitro-2H,2'H-3,3'-bi-1,2,4-triazole.
High-Density Energetic Metal-Organic Frameworks Based on the 5,5'-Dinitro-2H,2'H-3,3'-bi-1,2,4-triazole.
复制标题
DOI：
10.3390/molecules22071068
复制
发表时间：
2017-06-26
期刊：
影响因子：
--
通讯作者：
Pang S
中科院分区：
文献类型：
--
作者：
Dong Y;Peng P;Hu B;Su H;Li S;Pang S
基于富氮配体的高能金属有机框架（MOF）是一类新兴的炸药，密度是影响含能材料性能的积极因素之一。因此，设计和合成高密度含能MOFs非常重要。在本工作中，Cu(II)与刚性多硝基杂环配体5,5'-二硝基-2H,2'H-3,3'-bi-1,2,4-三唑(DNBT)和5,5'-二硝基-3,3'-双-1,2,4-三唑-1-二醇(DNBTO)的水热反应得到了两种高密度MOF：[Cu(DNBT)(ATRZ)3]n (1) 和 [Cu(DNBTO)(ATRZ)2(H2O)2]n (2)，其中 ATRZ 代表 4,4'-偶氮-1,2,4-三唑。通过红外光谱、元素分析、紫外可见吸收光谱和单晶X射线衍射对结构进行了表征。还通过热重/差示扫描量热分析（TG/DSC）测定了它们的热稳定性。结果表明，配合物 1 具有二维多孔框架，具有最稳定的椅式构象（如环己烷），而配合物 2 具有一维聚合结构。与之前报道的基于铜离子的MOF相比，该配合物具有更高的密度（配合物1的ρ = 1.93 g cm−3，配合物2的ρ = 1.96 g cm−3）和高热稳定性（配合物1的分解温度为323 °C，配合物2的分解温度为333.3 °C），特别是因为配合物2中引入了N-O键。我们预计这两种配合物将成为潜在的高能配合物密度材料。
High-energy metal–organic frameworks (MOFs) based on nitrogen-rich ligands are an emerging class of explosives, and density is one of the positive factors that can influence the performance of energetic materials. Thus, it is important to design and synthesize high-density energetic MOFs. In the present work, hydrothermal reactions of Cu(II) with the rigid polynitro heterocyclic ligands 5,5′-dinitro-2H,2′H-3,3′-bi-1,2,4-triazole (DNBT) and 5,5′-dinitro-3,3′-bis-1,2,4-triazole-1-diol (DNBTO) gave two high-density MOFs: [Cu(DNBT)(ATRZ)3]n (1) and [Cu(DNBTO)(ATRZ)2(H2O)2]n (2), where ATRZ represents 4,4′-azo-1,2,4-triazole. The structures were characterized by infrared spectroscopy, elemental analysis, ultraviolet-visible (UV) absorption spectroscopy and single-crystal X-ray diffraction. Their thermal stabilities were also determined by thermogravimetric/differential scanning calorimetry analysis (TG/DSC). The results revealed that complex 1 has a two-dimensional porous framework that possesses the most stable chair conformations (like cyclohexane), whereas complex 2 has a one-dimensional polymeric structure. Compared with previously reported MOFs based on copper ions, the complexes have higher density (ρ = 1.93 g cm−3 for complex 1 and ρ = 1.96 g cm−3 for complex 2) and high thermal stability (decomposition temperatures of 323 °C for complex 1 and 333.3 °C for complex 2), especially because of the introduction of an N–O bond in complex 2. We anticipate that these two complexes would be potential high-energy density materials.
登录
查看更多内容
影响因子：
2.4
作者：
Schmidt, RD;Lee, GS;Gilardi, R
通讯作者：
Gilardi, R
影响因子：
15
作者：
Goebel, Michael;Karaghiosoff, Konstantin;Stierstorfer, Joerg
通讯作者：
Stierstorfer, Joerg
影响因子：
--
作者：
Qi, Cai;Li, Sheng-Hua;Pang, Si-Ping
通讯作者：
Pang, Si-Ping
影响因子：
16.6
作者：
Li, Shenghua;Wang, Yuan;Pang, Siping
通讯作者：
Pang, Siping
影响因子：
4.6
作者：
Seth, Saona;Matzger, Adam J.
通讯作者：
Matzger, Adam J.