含能配合物研究进展综述

绿色、含能、钝感的含能化合物是近年来含能材料领域的研究热点。本文综述了近年来以呋咱类、唑类、吖嗪类等有机含能化合物为配体的含能配合物的合成、热行为及性能的研究状况。同时也描述了含有具有爆炸性质的阴离子如高氯酸根、叠氮根的配合物的研究现状,并展望了未来含能配合物研究发展方向。     

一种新型起爆药的合成

含能材料在民用、军事等多个领域都有广泛的应用。近年含能材料的研究主要集中在高氮类、高氣酸类、硝酸类、硝基酚类等化合物。高氮类含能材料是国内新型含能材料的研究热点之一。与传统的含能材料相比,高氮类含能材料具有更优良的爆轰性能,而且爆轰产物环保性能更好。含氮量高的火工药剂在燃烧时对枪管的烧蚀程度会明显低于含破量高的火工药剂。本文通过以高含氮量的4,4'-偶氮-1,2,4-三唑(atrz)为配体,结合三种不同金属盐制备了多氮金属配合物,并采用如外光谱分析法对其进行了结构表征,借用摩擦感度仪与撞击感度仪对三种配合物的爆炸性能进行测试,研究发现均具有很好的爆炸性能。     

基于巯基三氮唑及其衍生物构筑配合物的研究进展

巯基三氮唑是一种含硫氮杂环有机化合物,由于具有多个配位点和较强的配位能力以及衍生物的多样性, 近些年在配位化合物、医药等方面受到广泛研究。本文按照取代基数目的不同将巯基三氮唑衍生物分为疏基三 氮唑、单取代巯基三氮唑、多取代巯基三氮唑、多臂巯基三氮唑衍生物,并按照分类系统地总结了近些年来这 类配体及其金属配合物的合成方法和结构特征方面的研究成果,同时介绍了其金属配合物在药物、功能材料方 面的应用。最后依据巯基三氮唑及其衍生物构筑配合物的研究现状,从配体、金属离子两方面对巯基三氮唑未 来的研究方向进行了展望。     

新型多氮含能材料概述

主要从合成、物化性能方面简述了几类多氮含能材料:氨基/硝基杂环氮–氧化物、含能叠氮化合物、高氮化合物、钝感多氮高能炸药。结合国内外发展现状,指出了多氮含能材料技术未来发展的主要方向。     

含二茂铁基Schiff碱及其金属 配合物的合成、表征及抑菌活性

通过双乙酰基二茂铁和水合肼合成双乙酰基二茂铁双肼腙配体,然后分别与Cu(Ⅱ),Ni(Ⅱ),Zn(Ⅱ),Pb(Ⅱ),Cd(Ⅱ)合成金属配合物。配体及其金属配合物通过摩尔电导、元素分析、IR和1HNMR进行了表征。所有化合物进行了抗菌活性测试,结果表明,化合物都具有一定的抗菌活性,金属配合物2a~2f比其配体有更高的抗菌活性,其中,CdL(CH3COO)2(2f)的抗菌活性最高。     

喹啉类席夫碱锌离子荧光探针的合成及性能

以喹啉-8-甲醛和苯甲酰肼为原料,合成了具有席夫碱结构的Zn~(2+)荧光探针N-(喹啉-8-亚甲基)苯甲酰肼(L),用FTIR、NMR对探针结构进行了表征,并对其检测Zn~(2+)的机理进行了考察。结果表明:化合物L对Zn~(2+)有优良的选择性,最大荧光波长为523 nm,对Zn~(2+)检测限为4.1×10-8mol/L。化合物L与Zn~(2+)形成了物质的量比为1∶1的配合物(L-Zn),其机理为三齿的配体通过喹啉氮原子、席夫碱亚胺氮原子和酰胺羰基氧原子与Zn~(2+)配位,形成稳定的稠环配合物。     

水杨醛缩对羟基苯甲酰肼及其配合物的荧光研究

将Schiff碱与金属盐在一定的条件下反应,生成了具有稳定的结构和生物活性的配合物.该类配合物被广泛应用于药学、催化和分析化学等领域.本实验设计合成了水杨醛缩对羟基苯甲酰肼Schiff碱配体(H2L)及其10种金属配合物.采用红外光谱、元素分析、热重-差热分析对Schiff碱配体及其配合物进行了表征.并对目标化合物的荧光活性进行了初步测定.     

丙二酰肼席夫碱及其金属配合物合成与表征

合成了丙二酰肼缩双水杨醛席夫碱配体及与Cu(Ⅱ)、Ni(Ⅱ)和Zn(Ⅱ)的金属配合物。用元素分析、IR、摩尔电导和电子光谱对所有化合物进行了表征．对席夫碱配体还进行了^1HNMR和MS结构表征．给出了化合物可能的空间结构。     

含吡咯亚胺铜配合物的合成、表征及晶体结构

合成了一种新型含吡咯亚胺铜配合物,用元素分析、红外光谱及X射线单晶衍射对其进行了表征。结构解析表明,每个铜配合物分子含有两个吡咯亚胺配体,每个配体用两个氮原子与中心金属铜离子螯合,每个铜离子均采取平面四边形构型与配体中的四个氮原子配位。     

米力农锌配合物的合成、拓扑结构及性质表征

本研究利用含氰基的米力农作为配体与叠氮化钠及氯化锌在水热条件下合成得到了一个新颖结构的米力农四唑配合物[Zn(Mitz)_2(H_2O)]_n(1)(Mitz=米力农四唑=2-甲基-6-氧-1,6-二氢-(3,4’-双吡啶)-5-四唑),中心金属离子ZnⅡ与来自一个配体吡啶环上的氮原子和另外两个不同配体四唑环上的1,4位氮原子及一个水分子配位形成了一个形成一个轻微扭曲的的四面体结构,四个配体分别通过吡啶环和四唑环上的氮以金属锌为节点首尾相连,再加上另一个配体上四唑环上的1和4位上的氮在金属间桥联,形成了一个四十四元大环。每个配体分别通过四唑上的1和4位的氮原子及吡啶环上的氮原子形成一个三齿配体与三个Zn配位,三个配位原子方向各异,由此使得整个结构沿着空间各个方向延伸,形成了一个新颖的拓扑结构。通过热重分析还发现配合物1在450℃后才开始逐渐解体,这说明它是一个较为稳定的化合物。     

A New Computer Code for Assessment of Energetic Materials with Crystal density,Condensed Phase Enthalpy of Formation,and Activation Energy of Thermolysis

Crystal density and enthalpy of formation of the condensed phase of energetic compounds are two important input parameters for the performance prediction in several computer codes for rapid hazard assessment of energetic materials. A novel easy‐to‐handle user‐friendly computer code in Visual Basic is introduced to predict these parameters for various energetic compounds including nitroaliphatics, nitrate esters, nitramines, polynitroarenes, and polynitroheteroarenes. The calculated values can be used as inputs for other thermochemical/hydrodynamic computer codes. This computer code is also able to calculate the activation energies of thermal decomposition of polynitroarenes and nitramines in condensed state. The number of carbon, hydrogen, oxygen, and nitrogen atoms and specification of some molecular fragments are input parameters for this code without using any experimental data. The new algorithms on the base of easy‐to‐get input parameters are tested for some new energetic compounds, which provide more reliable results as compared to the best available methods.     

The development of controllable complex curing agents for epoxy resins. I. Preparation,characterization, and storage behavior of transition metal–diamine complexes

A series of complexes incorporating diamine (o‐phenylene diamine and 2‐aminobenzylamine—OPD and 2‐ABA respectively) ligands and containing the acetato and chloro transition metal salts of Ni and Cu has been prepared and characterized using elemental analysis and spectroscopic methods. Infrared data show that complexation of the amino nitrogen atoms occurs to a high degree. The same curing agents have been incorporated into two commercial epoxy resins recognized as “industry standards” (MY721 and MY750), and their cure properties and shelf life assessed alongside commercial curative systems. The current work demonstrates that while complexes based on copper(II) and nickel(II) and containing OPD ligands may be prepared and incorporated into commercial epoxy resins, there are some advantages associated with using 2‐ABA (as the diamine ligand) due to the higher complex solubility and better processing characteristics that it imparts to the formulated system. In general, the 2‐ABA based complexes disperse well within commercial epoxy systems and display good storage stability over prolonged periods of time (up to 67 days at ambient temperature). Work continues to examine the thermal and mechanical characteristics of commercial epoxy resins cured using these complexes. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1489–1503, 2001     

Preparation,Crystal Structure and Explosive Properties of Copper(II) Perchlorate Complex with 4‐Amino‐1,2,4‐Triazole and Water

A complex from copper(II) perchlorate with 4‐amino‐1,2,4‐triazole (4‐AT, C₂H₄N₄) was synthesized, and elemental composition, molecular structure, and explosive properties were determined. To this end, elemental and X‐ray analyses were carried out, sensitivity to mechanical and thermal stimuli was measured, mechanism of thermal decomposition was investigated, and kinetic parameters of decomposition were determined. In the next step measurements of heat of combustion and detonation velocity were performed. Detonation parameters were also calculated. It was stated that the complex has slightly distorted square bipyramidal (4+2) coordination. The four basal bonds are formed by nitrogen atoms of four 4‐AT molecules. The coordination of the metal is completed by two axial oxygen atoms, one of the perchlorate ion, and one of the water molecule. With respect to explosive properties, tetrakis(4‐AT)copper(II) perchlorate monohydrate belongs to the group of sensitive secondary explosives.     

5,5′-偶氮四唑过渡金属含能配合物对RDX和HMX热分解行为的影响

用DSC研究了5种5,5′-偶氮四唑过渡金属配合物MATZ(H2O)n(M=Mn,Ni,Zn,n=6;M=Co,Pb,n=3;ATZ=5,5′-偶氮四唑离子)对RDX和HMX热分解行为的影响。用分解峰温、热爆炸临界温度等特征参数评价了含配合物的二元混合物与纯组分的热分解行为。结果表明,配合物对RDX的影响大于对HMX的。含配合物的二元混合物的热分解行为与纯组分的热分解行为类似,配合物的分解影响了RDX和HMX的热分解特征参数。     

理论研究Cu(Ⅱ)对甘二肽分子的作用

采用B3LYP/6-31++G**方法研究了Cu(Ⅱ)对甘二肽分子的作用。优化得到16种稳定的配合物构型,探讨了配位型式和配位原子的相对活性,阐述了Cu(Ⅱ)对甘二肽性质的影响。主要结果如下:Cu(Ⅱ)与甘二肽之间的作用很强,结合能达到-1 154.45 kJ/mol;最稳定配合物是三齿配位的平面四边形结构,配位原子是两个N原子和羧基O原子;甘二肽中配位点的活性次序为:羧基O>氨基N>羟基O>亚氨基N>羰基O;Cu(Ⅱ)作用于甘二肽后,既利于羧基H的解离;又有利于亚氨基H的解离。     

First-principle study of nitrogen incorporation in amorphous carbon

First-principle calculations using quantum-mechanical density functional theory are carried out to study nitrogen incorporation in amorphous carbon, in which the structural models from liquid quench containing 64 atoms are introduced. The properties simulated for N incorporated amorphous carbon are in agreement with the available experimental results. The topological and electronic properties for nitrogen incorporation structures with various densities are investigated, and it is found that the bonding configuration of nitrogen atoms strongly depends on the density and the nitrogen concentration in the network. The simulations provide a qualitative support for a low nitrogen doping efficiency observed in the experiment since no true doping (N atoms substitutionally occupy C sites, leading to a donor level below conduction band mobility edge E_c) exists in any cases studied. For the tetrahedral amorphous carbon (at density of 2.9 g/cm³) with a low concentration of nitrogen (1.6 at% and 3.2 at%), the incorporated N atoms are found to adopt the auto-compensated sites or to be in threefold coordination. In particular, a new threefold C defect is found, which is introduced by nitrogen auto-compensation. Nitrogen incorporated amorphous carbon (2.0 g/cm³) leads to the formation of a graphite-like structure with twofold nitrogen coordination.     

静态与动态高压对含能材料热分解的影响

利用常压和高压差示扫描量热仪（DSC、PDSC）在动态和静态状下研究了CL-20、HMX、RDX、NC、NG、NG NC等几种含能材料的热分解,探讨了常压与高压条件下,静态与动态对这些含能材料热分解的影响。结果显示含能材料热分解受压力和动态气氛的影响有三种情况：1、热分解同时受到压力和动态气氛的影响;2、热分解既不受压力也不受动态气氛的影响;3、热分解只受压力的影响而不受动态气氛的影响。     

The Effects of Percent and Position of Nitrogen Atoms on Electronic and Thermoelectric Properties of Graphene Nanoribbons

Graphene-based nanostructures exhibit electronic properties that are not present in extended graphene. Graphene nanoribbons (GNRs) are expected to display extraordinary properties in the form of nanostructures. The effect of percent and position of nitrogen atoms on electronic and thermoelectric properties of a GNR is studied using Landauer approach and density functional theory. For this purpose the density of States, electronic current and thermal current have been calculated. Moreover, an analytical model for the thermo-conductance of the nanosized junction in two-dimensional graphene nanosystems developed. The results show that increasing of nitrogen atoms, increases the splitting of p-orbitals as well as band gap at Fermi level. Also the presence of nitrogen impurities is shown to yield resonant backscattering, whose features are strongly dependent on the position of the dopants. It is demonstrated that increasing N concentration decrease the thermal conductivity due to multi-scattering. In addition I–V characteristics exhibit robust nonlinear behaviors, which are strongly dependent on the position and theconcentration of the nitrogen atoms.     

含硫金属有机配合物的研究进展

综述了含硫金属有机配合物的研究进展，总结了巯基氮杂环配体的配位结构。表现在成键方式和分子结构上，极具丰富多样性。对于开展金属含硫配体配合物的合成与表征工作意义重大而深远。