Jujam Manojkumar, Rajak Richa, Kumar Navaneet, Ghule Vikas D, Dharavath Srinivas
Energetic Materials Laboratory, Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur, Uttar Pradesh, 208016, India.
Department of Chemistry, National Institute of Technology Kurukshetra, Kurukshetra, Haryana, 136119, India.
Chemistry. 2025 Aug 1;31(43):e202501984. doi: 10.1002/chem.202501984. Epub 2025 Jul 14.
Modern high-performing insensitive energetic materials are becoming more and more in demand to meet the growing needs of civilians and military applications. Here, the self-assembly of azole-based energetic molecules was described to construct potassium- and sodium-based energetic metal-organic frameworks (E-MOFs) using polyazole-based energetic 5,5'-(2-((1H-tetrazol-5-yl)methyl)-2H-1,2,3-triazole-4,5-diyl)bis(1H-tetrazole) (TBTT) linker. The X-ray analysis authenticates K-MOF (1) and Na-MOF (2), introducing hydrogen-bonded 3D frameworks. Both compounds were extensively studied by thermogravimetric analysis-differential scanning calorimetry (TGA-DSC), elemental analysis (EA), infrared spectroscopy (IR), Scanning Electron Microscopy (SEM), dynamic light scattering (DLS), and powder X-ray diffraction analyses (PXRD). Further, mechanical sensitivity, detonation properties, and Hirshfeld surface analyses were examined. As expected, both E-MOFs showed excellent thermal decomposition temperature (T 333-387 °C), which exceeds benchmark explosives like hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) (210 °C), 2,4,6-trinitrotoluene (TNT), hexanitrostilbene (HNS) (318 °C), and 2,4,6-triamino-1,3,5-trinitrobenzene (TATB) (315 °C). They also have shown high positive heat of formation (HOF = 366-525 kJ/mol) and superior detonation performance (VOD = 6857-8903 m/s; DP = 17.41-28.23 GPa). Additionally, the two E-MOFs exhibited low sensitivity toward impact sensitivity (IS > 60 J) and friction sensitivity (FS > 360 N), which may be attributed to strong structural reinforcement and multiple hydrogen bonding interactions, which is also proven by Hirshfeld surface analyses. Moreover, the high covalent bonds are beneficial in strengthening the E-MOF structures, which require high energy to collapse, thereby sustaining excellent thermal stability. E-MOFs 1 and 2 exhibit high iodine encapsulation and recyclability, maintaining effectiveness over six cycles, making them ideal for water remediation. Thus, compounds 1 and 2 can serve as promising next-generation highly thermally stable energetic materials, which can be a perfect replacement for currently used conventional explosives RDX, HNS, and TATB.
为满足民用和军事应用不断增长的需求，现代高性能钝感含能材料的需求日益增加。在此，描述了基于唑类的含能分子的自组装，以使用基于聚唑的含能5,5'-(2-((1H-四唑-5-基)甲基)-2H-1,2,3-三唑-4,5-二基)双(1H-四唑)(TBTT)连接体构建基于钾和钠的含能金属有机框架(E-MOFs)。X射线分析验证了K-MOF(1)和Na-MOF(2)，引入了氢键连接的三维框架。通过热重分析-差示扫描量热法(TGA-DSC)、元素分析(EA)、红外光谱(IR)、扫描电子显微镜(SEM)、动态光散射(DLS)和粉末X射线衍射分析(PXRD)对这两种化合物进行了广泛研究。此外，还研究了机械敏感性、爆轰性能和 Hirshfeld 表面分析。正如预期的那样，两种E-MOFs均表现出优异的热分解温度(T 333-387°C)，超过了基准炸药，如六氢-1,3,5-三硝基-1,3,5-三嗪(RDX)(210°C)、2,4,6-三硝基甲苯(TNT)、六硝基芪(HNS)(318°C)和2,4,6-三氨基-1,3,5-三硝基苯(TATB)(315°C)。它们还表现出高的正生成热(HOF = 366-525 kJ/mol)和优异的爆轰性能(VOD = 6857-8903 m/s；DP = 17.41-28.23 GPa)。此外，这两种E-MOFs对冲击敏感性(IS > 60 J)和摩擦敏感性(FS > 360 N)表现出低敏感性，这可能归因于强大的结构增强和多重氢键相互作用，Hirshfeld表面分析也证明了这一点。此外，高共价键有利于加强E-MOF结构，其坍塌需要高能量，从而保持优异的热稳定性。E-MOFs 1和2表现出高碘封装和可回收性，在六个循环中保持有效性，使其成为水修复的理想选择。因此，化合物1和2可作为有前途的下一代高热稳定性含能材料，可完美替代目前使用的传统炸药RDX、HNS和TATB。
