含能盐和含能离子液体

近年来含能盐和含能离子液体由于其独特的性质而受到广泛关注。本文综述了多种含能盐和含能离子液体（阳离子包括三唑、四唑、双环唑、六次甲基四胺等;阴离子包括硝酸根、高氯酸根、硝基唑、叠氮根、四硝基铝、多腈基化合物、二硝基尿素等）的合成;结合其表征结果分析了阳离子上的取代基以及阴阳离子对它们的性能如熔点、生成焓、密度等的影响。对含能盐和含能离子液体在炸药和推进剂方面的应用进行了展望。     

高氮化合物及其含能材料*

高氮含能化合物及其含能材料是新型含能材料领域的研究热点之一。相比于传统的含能材料,高氮含能材料具有很多优异或独特的理化性能和爆轰性能。本文综述了新型高氮化合物及其含能材料的研究进展,介绍了国内外近十年来众多研究小组的相关工作,重点阐述了四嗪、四唑和呋咱3大类高氮含能化合物的合成、性能及应用研究进展。结合作者的研究工作,进一步探讨了高氮含能化合物在钝感高能炸药、推进剂和新型气体发生剂等含能材料领域中的应用前景。     

可作起爆药的四唑金属含能配合物的合成及性能研究概况

含能金属配合物在国防领域具有重要意义和良好的应用前景,国内外对四唑类高氮金属含能配合物在用作起爆药方面的研究仍处于初步研究阶段。为了提高起爆药的使用性能和安全性,有必要了解先进高氮金属含能配合物的研究进展,以四唑衍生物为配体的配合物(尤其是5R-四唑阴离子为配体的含能配合物),有望在起爆药方面得到很好的发展,了解它们的合成和性能研究情况,挖掘其在含能材料特别是起爆药领域的应用潜力,有利于进一步探讨其结构与性能。     

环硅氮烷的合成与应用研究进展(1)——环二硅氮烷

环二硅氮烷是有机硅氮化合物中结构与性能比较特殊的一类化合物,在材料化学及配位化学领域有重要的潜在应用前景.综述了近年来环二硅氮烷的合成方法与应用研究进展.在合成方面,主要分为3条路线,分别由环三硅氮烷锂盐、取代硅胺及六氯化二硅为起始物.在应用领域,介绍了环二硅氮烷的离子开环聚合、等离子聚合、与其它单体的共聚、水解和金属配合物的制备及其在陶瓷、粘合剂和预想的催化剂上的应用.     

富氮唑类金属配合物的设计合成及应用

含能材料是一种特殊的能源材料,在国防和民用领域均具有特殊而重要的地位.富氮唑类合能金属配合物及其聚合物是含能材料的一个重要分支,它们在含能材料的起爆药、高能炸药、火箭推进剂和烟花等诸多领域均具有重要的研究价值和广阔的应用前景.本文从咪唑、吡唑、三唑、四唑和五唑等氮唑类含能金属配合物的理论设计、实验合成、性能评估和应用领...     

杂多蓝研究的进展

杂多酸及其盐类以其特有的结构和物理化学性质,已经成为一类有广阔应用前景的酸型和氧化还原型催化剂,在催化领域越来越引人关注。杂多蓝是杂多酸及其盐的还原产物,由于杂多酸及其盐被还原后,大多数呈现深蓝色,所以习惯上称为“杂多蓝”(Heteropoly     

硝基唑类含能化合物的合成研究进展

硝基唑类化合物在含能材料领域中应用较为广泛.按直接硝化、间接硝化、硝基重排、其他方法将硝化方法进行分类,综述了吡唑、咪唑、三唑及四唑硝基衍生物的合成,并介绍了一些重要硝基唑类含能化合物的特性及主要应用.     

3,6-双(1氢-1,2,3,4-四唑-5-氨基)-1,2,4,5-四嗪的合成与表征

研究了低感度高氮化合物3,6-双(1氢-1,2,3,4-四唑-5-氨基)-1,2,4,5-四嗪的合成,其结构经元素分析,IR,^1H NMR和^13C NMR表征。     

基于全氟烷基磺酰亚胺催化剂合成、固载及催化应用研究进展

普通的液体酸催化剂在应用过程中难免产生环境问题,全氟烷基磺酰亚胺配合物因其特殊的阴离子结构以及所具有的超酸性质而在新型催化领域表现出广泛的应用前景.介绍了全氟烷基磺酰亚胺配合物的结构与性能特点,综述了近年来全氟烷基磺酰亚胺及其配合物的制备方法,重点阐述了全氟烷基磺酰亚胺及其配合物固载化的方法及在催化反应中的最新研究进展,以期对其催化性能和应用前景有比较全面的认识.     

四唑类化合物的合成及应用研究新进展

四唑是一种重要的五元芳杂环,具有多氮富电子的平面结构特征.这种特殊的结构使得四唑类化合物作为药物、炸药、功能材料等在医学、农学、材料科学等众多领域具有广泛的应用前景.相关研究十分活跃,已取得了许多重要进展.结合作者唑类方面的研究,参考国内外近五年文献,系统地综述了四唑类化合物的合成及其在医药、农药、材料等领域的应用研究新近况.     

Modification of sulfonated polyphenylquinoxaline by alkali and alkaline earth metal cations

Salts of sulfonated polyphenylquinoxaline (SPPQ) containing alkaline earth metal ions—Mg²⁺, Ca²⁺, and Ba²⁺—were synthesized. The paper considers their solubilities, the properties of solutions, and thermal stability in comparison with analogous characteristics of SPPQ salts with alkali metals. The introduction of alkaline earth metal cations into SPPQ affords soluble polymeric salts having high thermal stability. Solutions of SPPQ salts in N-methylpyrrolidone (N-MP) containing Mg²⁺, Ca²⁺, and Ba²⁺ ions do not exhibit polyelectrolyte properties, unlike solutions of SPPQ salts in which the counterions are Li⁺, Na⁺, and K⁺. Solutions of SPPQ and its salts in N-MP can be converted to water-soluble form by dialysis. This opens up new prospects for using the polymeric salts.     

Elucidation of the Alternating Copolymerization Mechanism of Epoxides or Aziridines with Cyclic Anhydrides in the Presence of Halide Salts

Organic halide salts in combination with metal or organic compound are the most common and essential catalysts in ring-opening copolymerizations (ROCOP). However, the role of organic halide salts was neglected. Here, we have uncovered the complex behavior of organic halides in ROCOP of epoxides or aziridine with cyclic anhydride. Coordination of the chain-ends to cations, electron-withdrawing effect, leaving ability of halide atoms, chain-end basicity/nucleophilicity, and terminal steric hindrance cause three types of side reactions: single-site transesterification, substitution, and elimination. Understanding the complex functions of organic halide salts in ROCOP led us to develop highly active and selective aminocyclopropenium chlorides as catalysts/initiators. Adjustable H-bonding interactions of aminocyclopropenium with propagating anions and epoxides create chain-end coordination process that generate highly reactive carboxylate and highly selective alkoxide chain-ends.     

Review: the multicolored coordination chemistry of violurate anions

This review provides a comprehensive overview on the coordination chemistry of violuric acid, C₄H₃N₃O₄ (= H₃Vio), and its derivatives (e.g. 1,3-diorganovioluric acids and thiovioluric acid). The most remarkable property of these colorless compounds is the formation of brightly colored (pantochromic/polychromic) salts with colorless cations such as alkali metal and alkaline earth metal ions and organoammonium ions. These magnificent colors have fascinated chemists for more than a century. Only in recent years it has been fully recognized that the structural chemistry of violurates is rather interesting and diverse. Violurate anions are excellent building blocks for new supramolecular assemblies in the crystalline state. Various organoammonium violurates and transition metal violurate complexes have been structurally characterized through single-crystal X-ray diffraction. Highly characteristic for these structures is the formation of 1D, 2D, or 3D hydrogen-bonded assemblies in the crystalline state. This review provides a comprehensive overview on the multicolored coordination chemistry of violurate anions, with the focus being on structurally characterized species.     

Coordination compounds of electron-deficient boron cluster anions BnH n2? (n = 6, 10, 12)

This survey concerns the coordination ability of B _n H _n ²⁻ (n = 6, 10, 12) boron cluster anions and their derivatives in complex formation. Boron cluster anions form four types of compounds: salts of organic cations and alkali-metal cations, including Cat₂B _n H _n , where specific interactions can be observed between a cation Cat and a boron cluster anion; salts of protonated anions CatB₆H₇ and CatB₁₀H₁₁, analogues of Cat[MB _n H _n ] complexes, where an extra hydrogen atom appears bound with the BBB face of a boron polyhedron and performs as a hard acceptor; metal complexes with outer-sphere boron cluster anions where specific ligand-ligand interactions may be observed between a boron cluster anion and an inner-sphere ligand; and true metal complexes with boron cluster anions that enter the inner coordination sphere. The last case characterizes closo-hydroborate anions as polydentate ligands whose denticity can vary widely under the effect of substituents or other ligands in the complex.     

Assembly of Tetrazolylfuroxan Organic Salts: Multipurpose Green Energetic Materials with High Enthalpies of Formation and Excellent Detonation Performance

A series of highly energetic organic salts comprising a tetrazolylfuroxan anion, explosophoric azido or azo functionalities, and nitrogen-rich cations were synthesized by simple, efficient, and scalable chemical routes. These energetic materials were fully characterized by IR and multinuclear NMR (¹H, ¹³C, ¹⁴N, ¹⁵N) spectroscopy, elemental analysis, and differential scanning calorimetry (DSC). Additionally, the structure of an energetic salt consisting of an azidotetrazolylfuroxan anion and a 3,6,7-triamino-7H-[1,2,4]triazolo[4,3-b][1,2,4]triazolium cation was confirmed by single-crystal X-ray diffraction. The synthesized compounds exhibit good experimental densities (1.57–1.71 g cm⁻³), very high enthalpies of formation (818–1363 kJ mol⁻¹), and, as a result, excellent detonation performance (detonation velocities 7.54–8.26 kms⁻¹ and detonation pressures 23.4–29.3 GPa). Most of the synthesized energetic salts have moderate sensitivity toward impact and friction, which makes them promising candidates for a variety of energetic applications. At the same time, three compounds have impact sensitivity on the primary explosives level (1.5–2.7 J). These results along with high detonation parameters and high nitrogen contents (66.0–70.2 %) indicate that these three compounds may serve as potential environmentally friendly alternatives to lead-based primary explosives.     

核磁共振波谱技术在室温离子液体研究中的应用*

室温离子液体作为一种绿色溶剂和功能材料,越来越引起人们的重视,其研究手段也越来越多。本文着重概述了核磁共振方法在测定离子液体的结构、纯度及性质,研究离子液体阴阳离子间的相互作用、离子液体与其他化合物的相互作用、离子液体及其在混合体系中的动力学特征、离子液体在溶液中的聚集行为,以及测定离子液体的热力学参数中的应用。     

A computational study of proton transfer and solvent effect on nitroamino[1,3,5]triazine-based ammonium energetic salts

We have performed dispersion corrected density functional theory calculations to study the proton transfer in the gas-phase and solvent effects on the structural transformation for a series of nitrogen-rich energetic salts. Proton transfer was observed from the cations to anions within all the salts in the gas-phase and resulted into neutral hydrogen-bonding complexes; however, they were stabilized as ionic structures in the liquid state with solvation energies in the range of ?37.72–69.37 kJ/mol. An increment by 4–9 Debye in the dipole moment was found when the salts went from the gas to solution. Moreover, these ionic salts exhibited relatively high densities in the range of 1.63–1.96 g/cm³ desirable for energetic materials. A combination of NH₃OH⁺ to the cation and ?NO₂ or ?NF₂ group to the anion can improve efficiently the detonation performance. Most of the ammonium, hydroxyammonium, and hydrazinium salts were promising competitive explosives and could be used as potential targets for synthesis.     

Octahedral rhenium(III) chalcocyanide cluster anions: Synthesis, structure, and solid state design

The review summarizes data on synthesis and structure of rhenium chalcocyanide cluster onions [ Re₆X₈(CN)₆]^4-f (X = S, Se, Te) belonging to a new class of inorganic compounds. Two main groups of such compounds are considered: salts with an island structure and polymer compounds. Various factors governing the type of structure and the dimensionality of the polymer compounds are analyzed, including the nature of the chalcogen atom in the cluster anion, preferable coordination of the transition metal cation, and the size of additional charge-compensating cations. Crystal-chemical approaches to design of complex salts based on octahedral rhenium chalcocyanide cluster anions are formulated. Translated fromZhurnal Strukturnoi Khimii, Vol. 41, No. 3, pp. 609-638, May–June, 2000.     

ELECTRON TRANSFER REACTIONS OF METAL CARBONYL ANIONS

Abstract

Metal carbonyl anions exhibit one- and two-electron reactions. The two-electron processes involving transfer of groups (hydrogen, alkyl, and halogen) between metal centers are related to the nucleophilicity. The one-electron processes are primarily outer-sphere electron transfer for the metal carbonyl anions. These reactions are observed in the presence of oxidants such as coordination complexes, pyridinium salts, metal carbonyl dimers and metal carbonyl clusters. However, in contrast to organic reactions, the metal carbonyl anions may undergo inner-sphere electron transfer. Reactions of metal carbonyl anions of low nucleophilicity with metal carbonyl cations or halides are best interpreted as inner-sphere, one-electron transfer.