Li Hui, Zhang Lei, Petrutik Natan, Wang Kangcai, Ma Qing, Shem-Tov Daniel, Zhao Fengqi, Gozin Michael
Science and Technology on Combustion and Explosion Laboratory, Xi'an Modern Chemistry Research Institute, Xi'an 710065, China.
School of Chemistry, Faculty of Exact Sciences, Tel Aviv University, Tel Aviv 69978, Israel.
ACS Cent Sci. 2020 Jan 22;6(1):54-75. doi: 10.1021/acscentsci.9b01096. Epub 2019 Dec 27.
Extensive density functional theory (DFT) calculation and data analysis on molecular and crystal level features of 60 reported energetic materials (EMs) allowed us to define key descriptors that are characteristics of these compounds' thermostability. We see these descriptors as reminiscent of "Lipinski's rule of 5", which revolutionized the design of new orally active pharmaceutical molecules. The proposed descriptors for thermostable EMs are of a type of molecular design, location and type of the weakest bond in the energetic molecule, as well as specific ranges of oxygen balance, crystal packing coefficient, Hirshfeld surface hydrogen bonding, and crystal lattice energy. On this basis, we designed three new thermostable EMs containing bridged, 3,5-dinitropyrazole moieties, , , and , which were synthesized, characterized, and evaluated in small-scale field detonation experiments. The best overall performing compound exhibited an onset decomposition temperature of 341 °C and has a density of 1.865 g cm, and the calculated velocity of detonation and maximum detonation pressure were 8517 m s and 30.6 GPa, respectively. Considering 's impressive safety parameters [impact sensitivity (IS) = 22 J; friction sensitivity (FS) = 352; and electrostatic discharge sensitivity (ESD) = 1.05 J] and the results of small-scale field detonation experiments, the proposed guidelines should further promote the rational design of novel thermostable EMs, suitable for deep well drilling, space exploration, and other high-value defense and civil applications.
通过对60种已报道的含能材料（EMs）的分子和晶体水平特征进行广泛的密度泛函理论（DFT）计算和数据分析，我们能够定义出这些化合物热稳定性特征的关键描述符。我们认为这些描述符让人联想到“Lipinski五规则”，该规则彻底改变了新型口服活性药物分子的设计。所提出的热稳定含能材料的描述符包括含能分子的分子设计类型、最弱键的位置和类型，以及氧平衡、晶体堆积系数、Hirshfeld表面氢键和晶格能的特定范围。在此基础上，我们设计了三种新型热稳定含能材料，它们含有桥连的3,5-二硝基吡唑基团，分别为[此处应给出具体化合物名称1]、[此处应给出具体化合物名称2]和[此处应给出具体化合物名称3]，并进行了合成、表征以及小规模野外爆轰实验评估。综合性能最佳的化合物[此处应给出具体化合物名称]的起始分解温度为341℃，密度为1.865 g/cm³，计算得到的爆速和最大爆压分别为8517 m/s和30.6 GPa。考虑到[此处应给出具体化合物名称]令人印象深刻的安全参数[撞击感度（IS）= 22 J；摩擦感度（FS）= 352；静电放电感度（ESD）= 1.05 J]以及小规模野外爆轰实验结果，所提出的指导方针应能进一步推动适用于深井钻探、太空探索以及其他高价值国防和民用应用的新型热稳定含能材料的合理设计。
