Midway between Energetic Molecular Crystals and High-Density Energetic Salts: Crystal Engineering with Hydrogen Bonded Chains of Polynitro Bipyrazoles,Crystal Growth & Design

当前位置： X-MOL 学术 › Cryst. Growth Des. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

Midway between Energetic Molecular Crystals and High-Density Energetic Salts: Crystal Engineering with Hydrogen Bonded Chains of Polynitro Bipyrazoles
Crystal Growth & Design ( IF 3.2 ) Pub Date : 2020-01-24 , DOI: 10.1021/acs.cgd.9b01177
Ivan Gospodinov ₁ , Kostiantyn V. Domasevitch ₂ , Cornelia C. Unger ₁ , Thomas M. Klapötke ₁ , Jörg Stierstorfer ₁

Affiliation

A new strategy for supramolecular synthesis of energetic salts is reported. It is still a challenge to address packing patterns and crystal morphologies of such materials due to the lack of reliable supramolecular synthons, which are applicable to polynitro substituted species. 3,5-Dinitro-4,4′-bipyrazole (1), 3,3′,5-trinitro-4,4′-bipyrazole (2), and 3,3′,5,5′-tetranitro-4,4′-bipyrazole (3) are excellent functional models that provide a higher degree of control over the structure by manipulating robust self-assembly molecular building blocks of lower dimensionality. A variety of K⁺, Cs⁺, and nitrogen-rich salts (e.g., ammonium, aminoguanidinium, hydrazinium, and hydroxylammonium) 4–17, prepared by single deprotonation of NH-acidic 1–3, are based upon polar anionic chains sustained with strong NH···N bonding of conjugate acidic and basic pyrazole/pyrazolate sites. A gradual increase of NH-acidity (dinitropyrazolyl > nitropyrazolyl ≫ pyrazolyl) productively contributes to the strength of NH···N bonds and reliability of such supramolecular synthon. New synthesized energetic materials were fully characterized by NMR (¹H, ¹³C, and ¹⁴N) spectroscopy, infrared spectroscopy, differential thermal analysis (DTA), and elemental analysis, and the heats of formation were calculated using the atomization method based on CBS-4 M enthalpies. Several detonation parameters, such as detonation pressure, velocity, and energy, were calculated by using the X-ray densities and the calculated standard molar enthalpies of formation. The sensitivities toward external stimuli were tested according to the BAM standards. In addition, the toxicity toward Vibrio fischeri bacteria of the monopotassium salt 9·H₂O is reported.

中文翻译：

高能分子晶体与高密度能盐之间的中途：具有多硝基联吡唑氢键键合的晶体工程

报道了一种超分子合成高能盐的新策略。由于缺乏适用于多硝基取代物质的可靠的超分子合成子，解决这类材料的堆积模式和晶体形态仍然是一个挑战。3,5-二硝基-4,4'-联吡唑（1），3,3'，5-三硝基-4,4'-联吡唑（2）和3,3'，5,5'-四硝基-4， 4'-联吡唑（3）是出色的功能模型，通过操纵低维稳健的自组装分子构建基块，可提供对结构的更高程度的控制。各种K ⁺，Cs ⁺和富氮盐（例如铵盐，氨基胍盐，肼盐和羟基铵盐）4 –17，通过NH-酸性的单脱质子制得1 - 3，是基于极性阴离子链缀合物具有酸性和碱性吡唑/吡唑特网的强NH ... N键持续。NH酸度的逐渐增加（二硝基吡唑基>硝基吡唑基≫吡唑基）有效地提高了NH···N键的强度和这种超分子合成子的可靠性。新合成的高能材料已通过NMR（¹ H，¹³ C和¹⁴N）光谱，红外光谱，差热分析（DTA）和元素分析，并使用基于CBS-4M焓的雾化方法计算形成的热量。通过使用X射线密度和计算的标准地层摩尔焓，计算了一些爆轰参数，例如爆轰压力，速度和能量。根据BAM标准测试了对外界刺激的敏感性。另外，据报道单钾盐9·H ₂ O对费氏弧菌具有毒性。

更新日期：2020-01-24

点击分享查看原文

点击收藏

阅读更多本刊新发论文本刊介绍/投稿指南