High Energetic Materials Research Articles

Laser Response Mechanism of Typical Ammonium-Nitrate and Furazan based Energetic Graphene Oxide Composites

Abstract Graphene oxide (GO) had been used for the energetic performance regulation of high energy density energetic materials (HEDMs), such as balancing the contradiction between high energy and high sensitivity of ammonium nitrate and furazan based energetic materials. However, GO based energetic composites shown photosensitization characteristics, which could bring risks to their safe application in novel battle environments. In this paper, cyclotrimethylnitrosamine (RDX), hexanitrohexazazane (CL-20), and 3,4-dinitrofurazanyl Furoxane oxide (DNTF) were taken as typical research objects to prepare their GO based energetic composites, and an evaluation method of laser response characteristics of energetic materials was established, the laser response characteristics and hot spot ignition mechanism of GO@RDX, GO@CL-20, and GO@DNTF were obtained. This work not only provided ideas for the safety design of energetic materials, but also provided support for applications such as reliable ignition output.

NiCoCr2O4 as a potential catalyst for the thermal decomposition of ammonium nitrate: a kinetic investigation

The thermal decomposition of high energetic materials plays an important role in their thermal performance. Use of the catalyst is one of the efficient ways improve the thermal performance of the high energetic materials. Therefore, in this work nickel cobalt chromite (NiCoCr2O4) prepared using precipitation approach was utilized as a catalyst for decreasing the thermal decomposition temperature and activation energy of high energetic material ammonium nitrate (AN). The results suggest that AN/NiCoCr2O4 decomposes at lower temperature (240 °C) within a short temperature range (Thermo gravimetry decomposition curve = 180–250 °C). The kinetic study was investigated using Kissinger-Akahira-Sunose (KAS) and Kissinger method (5, 10, and 15 °C min−1 heating rates). The activation energy of AN was reduced from 158.0 to 141.5 kJ mol−1 and decrease in the pre-exponential factor was observed upon addition of NiCoCr2O4. The outcome of the present work can be used to design AN based high energetic formulations containing NiCoCr2O4 catalyst with better thermal decomposition performance.

Preparation, characterization, and investigation of thermal behavior of improved HMX and RDX through coating by TNT

ABSTRACT Simultaneous achievement of both low sensitivity and high energy is crucial in practical applications of high energetic materials such as HMX and RDX. In this work, TNT, a low-sensitive explosive, was used to improve sensitivity and thermal stability of HMX and RDX explosives. The method is based on coating HMX and RDX with TNT using solvent-anti-solvent technique. The characterization of samples was done by scanning electron microscopy (SEM), transmission electron microscope (TEM), and X-ray diffraction (XRD). The SEM and TEM images revealed that a layer of TNT was coated on the HMX and RDX surfaces. TG/DSC thermograms for HMX/TNT and RDX/TNT show that decomposition enthalpy change (ΔH) increased to 121.1 and 197.6 J/g compared to pure HMX and RDX, respectively. Fluidity test results showed that the fluidity of the samples improved from medium to good grade after coating. The impact sensitivity for HMX/TNT and RDX/TNT improved to 7.35 and 19.62 J, respectively. Also, friction sensitivity for coated HMX and RDX increased to 210.2 and 196.1 N. The electrostatic discharge experiments showed that HMX/TNT and RDX/TNT were safer than pure HMX and RDX. Therefore, the coated samples will be good candidates for energetic formulations.

Density functional theory (DFT) study on the structures and energy properties of high energy density materials based on polynitroazofurazan derivatives

In this study, inspired by the structures of the heat resistant explosives 5,5’-bis(2,4,6-trinitrophenyl)-2,2′-bi(1,3,4-oxadiazole) and 2,6-bis(picrylamino)-3,5-dinitro-pyridine, five high energy and low sensitivity energetic materials have been designed by combining the energetic fragments with the high energy azofurazan skeleton, and structure - property relationships have been investigated by means of density function theory. All compounds have excellent explosive properties (Dv: 7946–8341 m/s; P: 27.6–30.9 GPa) and high positive heats of formation (816.85–940.28 kJ/mol). Among them, compounds 3 and 4 have the best explosive properties (3: Dv: 8318 m/s P:30.7 GPa; 4: Dv: 8341 m/s P: 30.9 GPa), which are comparable to 1,3,5-trinitrohexahydro-1,3,5-triazine. The h50 values indicate that all compounds have good impact sensitivity, comparable to 1,3,5,7-tetranitro-1,3,5,7-tetrazocane and 1,3,5-trinitrohexahydro-1,3,5-triazine and superior to hexanitrohexaazaisowurtzitane. In addition, bond dissociation energies, frontier molecular orbitals, and weak interaction, etc. are calculated to further investigate the relationship between structures and properties. The calculated results show that these compounds are expected to be the next generation of high energy density materials with an excellent balance of energetic properties and stability.

Preparation and safety study of TKX-50/CL-20 composite explosives

ABSTRACT CL-20, as the best comprehensive high nitrogen energetic material, plays an important role in weaponry, equipment, and national defense. TKX-50, as a new type of ionic explosive, is commonly used for composite explosives due to its excellent desensitization effect. This work combines TKX-50 and CL-20, and then encapsulates them using demulsification method. TKX-50/CL-20 composite explosives were successfully prepared at the binder dosage of only 1.5 wt.%, which showed good encapsulation effects. The results showed that the Polyvinyl butyraldehyde (PVB) and wax were successfully coated on the surface of the explosive particles, and the crystal structure of CL-20 in the composite did not change, while the excellent detonation property of ε-CL-20 is retained. Our study found that TKX-50 has a catalytic effect on the decomposition of CL-20, and when mixed alone, the activation energy of CL-20 is significantly reduced. Furthermore, the activation energy of the TKX-50/CL-20 composite explosive prepared has hardly changed compared to CL-20, and it has better thermal stability compared to TKX-50/CL-20 (1:1). The impact sensitivity and friction sensitivity of TKX-50/CL-20 composite explosives have also been significantly improved, with 2 J and 96 N higher than the TKX-50/CL-20 (1:1) raw materials, respectively, demonstrating good desensitization effect.

Efficient Synthesis, Characterization, and DFT Calculation of 4,4’-Azo-1,2,4-triazole

ABSTRACT 4,4’-Azo-1,2,4-triazole (atrz) is a new high nitrogen energetic material with high energy density, high gas yield and wide application prospects, but the low synthesis temperature and long time are the main reasons limiting its application. To achieve efficient synthesis of atrz, the double drop synthesis method was designed to solve the problem of unstable concentration of oxidant (HClO) due to batch feeding. The reaction temperature, reaction time, and molar ratio of reactants of n(4-amino-1,2,4-triazole):n(ClO−) were studied and optimized using the single factor variable method; Characterization and analysis of atrz using theoretical calculations with elemental analysis, infrared spectroscopy, crystal morphology, and nuclear magnetic resonance; The thermal properties and stability of atrz were tested and analyzed using TG-DTA. The results showed that the reaction time of the double drop synthesis method was shortened from 5 hours to 1.5 hours under the conditions of similar yield, and the efficiency was increased by 2.3 times. The optimized process was a reaction temperature of 5°C-10°C, reaction time of 1.5 hours, n(4-amino-1,2,4-triazole):n(ClO−) of 1:2, and the yield reached 73%. The product was white, needle-like crystals, which were determined to be atrz by means of characterization and theoretical calculations. Atrz’s decomposition peak temperature is 309.0°C, and when the temperature is below 271.7°C, atrz is thermally stable. The activation energies of atrz calculated by Kissinger and Flynn-Wall-Ozawa methods were 195.0 kJ·mol−1 and 194.6 kJ·mol−1.

Methodology for Studying Combustion of Solid Rocket Propellants using Artificial Neural Networks

The combustion properties of energetic materials have been extensively studied in the scientific literature. With the rapid advancement of data science and artificial intelligence techniques, predicting the performance of solid rocket propellants (SRPs) has become a key focus for researchers globally. Understanding and forecasting the characteristics of SRPs are crucial for analyzing and modeling combustion mechanisms, leading to the development of cutting-edge energetic materials. This study presents a methodology utilizing artificial neural networks (ANN) to create multifactor computational models (MCM) for predicting the burning rate of solid propellants. These models, based on existing burning rate data, can solve direct and inverse tasks, as well as conduct virtual experiments. The objective functions of the models focus on burning rate (direct tasks) and pressure (inverse tasks). This research lays the foundation for developing generalized combustion models to forecast the effects of various catalysts on a range of SRPs. Furthermore, this work represents a new direction in combustion science, contributing to the creation of a High-Energetic Materials Genome that accelerates the development of advanced propellants.

An ab Initio Study of High-Energetic Trioxatriazinane Derivatives: Conformational Analysis, Nitrogen Inversion, Heats of Formation, Dissociation Reaction, and Dimerization.

High-energetic materials belong to two main classes: propellants and explosives. The still rather unexplored family of 1,3,5,2,4,6-trioxatriazinanes, N3O3R3, has a representative of each class. We have selected three compounds, R = H, R = CH3 and R = NO2, this last compound being known as TNTOTA, "trinitro-trioxa-triazinane". Of these compounds we have studied the conformational analysis, the nitrogen inversion, the heats of formation, and the dissociation reaction into the three monomers. In addition, the corresponding 1,3,2,4-dioxadiazetidines (N2O2R2) have also been studied.

Host-Guest Technique for Designing Highly Energetic Compounds with the Nitroamino Group.

A new energetic material, 2-azido-4,7-nitroamino-1H-imidazo[4,5-d]pyridazine (ANIP) with a highly sensitive azido group and its host-guest compounds (ANIP/H2O and ANIP/H2O2), and energetic salts were obtained. With the guest and protons in host molecules, an abundant hydrogen bond system can be formed. This results in high crystal density and good sensitivity, which suggests that the host-guest strategy is a promising way to balance the contradiction between energy and sensitivity and provides a new path to obtain a new generation of high energetic materials.

Determining the mechanical and decomposition properties of high energetic materials (α-RDX, β-HMX, and ε-CL-20) using a neural network potential.

Molecular simulations of high energetic materials (HEMs) are limited by efficiency and accuracy. Recently, neural network potential (NNP) models have achieved molecular simulations of millions of atoms while maintaining the accuracy of density functional theory (DFT) levels. Herein, an NNP model covering typical HEMs containing C, H, N, and O elements is developed. The mechanical and decomposition properties of 1,3,5-trinitroperhydro-1,3,5-triazine (RDX), hexahydro-1,3,5-trinitro-1,3,5-triazine (HMX), and 2,4,6,8,10,12-hexanitrohexaazaisowurtzitane (CL-20) are determined by employing the molecular dynamics (MD) simulations based on the NNP model. The calculated results show that the mechanical properties of α-RDX, β-HMX, and ε-CL-20 agree with previous experiments and theoretical results, including cell parameters, equations of state, and elastic constants. In the thermal decomposition simulations, it is also found that the initial decomposition reactions of the three crystals are N-NO2 homolysis, corresponding radical intermediates formation, and NO2-induced reactions. This decomposition trajectory is mainly divided into two stages separating from the peak of NO2: pyrolysis and oxidation. Overall, the NNP model for C/H/N/O elements in this work is an alternative reactive force field for RDX, HMX, and CL-20 HEMs, and it opens up new potential for future kinetic study of nitramine explosives.

First-principles study on the structure and stability of (H<sub>2</sub>dabco)[K(ClO<sub>4</sub>)<sub>3</sub>] under hydrostatic pressure

The crystal structure, molecular structure, electronic structure and mechanical properties of molecular perovskite high-energetic material (H<sub>2</sub>dabco)[K(ClO<sub>4</sub>)<sub>3</sub>] (DAP-2) under hydrostatic pressure ranging from 0 to 50 GPa are calculated and studied based on density functional theory. And the influences of pressure on its stability and impact sensitivity of DAP-2 are investigated. As the external pressure gradually increases, both the lattice parameters and the volume of DAP-2 crystal exhibit a monotonic decreasing trend. In the entire pressure range, the unit cell volume shrinks by up to 40.20%. By using the Birch Munnaghan equation of state to fit <i>P</i>-<i>V</i> relation, the bulk modulus <i>B</i><sub>0</sub> and its first-order derivative <i>B</i><sub>0</sub>’ with respect to pressure are obtained to be 23.4 GPa and 4.9 GPa, respectively. The observations of the characteristic bond length and bond angle within the crystal indicate that the cage-like structure of organic cation H<sub>2</sub>dabco<sup>2+</sup> undergoes distortion at 25 GPa. Further analysis of the average fractional coordinates of the center-of-mass and Euler angles for H<sub>2</sub>dabco<sup>2+</sup> and KO<sub>12</sub> polyhedron shows that within a pressure range from 0 to 50 GPa, both the average fractional coordinates of the center-of-mass and the Euler angles exhibit fluctuations at 25 GPa, but the overall amplitude of these fluctuations is very small. Based on this finding, it is speculated that the space group symmetry of the crystal may remain unchanged in the entire pressure range. In terms of electronic structure, with the increase of pressure, the band gap value increases rapidly and reaches a maximum value at about 20 GPa, followed by a slow decreasing trend. Based on the first-principles band gap criterion and the variation of the band gap under different pressures, it is demonstrated that below 20 GPa, the impact sensitivity of DAP-2 gradually decreases with pressure increasing; however, when the pressure exceeds 20 GPa, the impact sensitivity exhibits a slow increasing trend. In addition, the elastic constants <i>C</i><sub><i>ij</i>,</sub> Young’s modulus (<i>E</i>), bulk modulus (<i>B</i>), shear modulus (<i>G</i>), and Cauchy pressure (<i>C</i><sub>12</sub> – <i>C</i><sub>44</sub>) all increase with pressure rising, indicating that the rigidity and ductility of the crystal under pressure are significantly strengthened. According to the mechanical stability criterion, the crystal maintains the mechanical stability throughout the pressure range.

Construction of core@double-shell structured energetic composites with simultaneously enhanced thermal stability and safety performance

The poor thermal stability and high sensitivity severely hinder the practical application of hexanitrohexaazaisowurtzitane (CL-20). Herein, a kind of novel core@double-shell CL-20 based energetic composites were fabricated to address the above issues. The coordination complexes which consist of natural polyphenol tannic acid (TA) and FeIII were chosen to construct the inner shell, while the graphene sheets were used to build the outer shell. The resulting CL-20/TA-FeIII/graphene composites exhibited simultaneously improved thermal stability and safety performance with only 1 wt% double-shell content, which should be ascribed to the intense physical encapsulation effect from inner shell combined with the desensitization effect of carbon nano-materials from outer shell. The phase transition (ε to γ) temperature increased from 173.70 °C of pure CL-20 to 191.87 °C of CL-20/TA-FeIII/graphene composites. Meanwhile, the characteristic drop height (H50) dramatically increased from 14.7 cm of pure CL-20 to 112.8 cm of CL-20/TA-FeIII/graphene composites, indicating much superior safety performance after the construction of the double-shell structure. In general, this work has provided an effective and versatile strategy to conquer the thermal stability and safety issues of CL-20 and contributes to the future application of high energy density energetic materials.

Thermal stability vs. energy content of compound: Thermolysis of tetrazino-tetrazine 1,3,6,8-tetraoxide (TTTO) from a broad perspective

Tetrazino-tetrazine 1,3,6,8-Tetraoxide (TTTO) is one of the most powerful energetic materials synthesized to date. Its thermal decomposition of [1,2,3,4]tetrazino[5,6-e][1,2,3,4]tetrazine 1,3,6,8-tetraoxide (TTTO) has been investigated for the first time. The obtained formal kinetic model of thermolysis includes the two-dimensional nucleation-growth with an activation energy of 102 ± 3 kJ mol−1 and the second-order reaction with barrier of 184 ± 4 kJ mol−1. Judged by the decomposition onset (155 °C), TTTO is the most thermally stable among known top energetic substances. A broader analysis of 360 energetic and non-energetic chemicals supports the idea of general thermal stability decrease with the molecule’s energy content rise, although the relationship is built as envelope of the cloud of experimental data. Two hypotheses for high energetic materials design are formulated: the limiting value of performance achieved with stable organic species (10% over benchmark 1,3,5,7-tetranitro-1,3,5,7-tetrazocane, HMX) and the existence of top performing molecules that are more thermally stable compounds than TTTO.

Prediction of Ethanol-Mediated Growth Morphology of Ammonium Dinitramide/Pyrazine-1,4-Dioxide Cocrystal at Different Temperatures.

The crystal morphology of high energetic materials plays a crucial role in aspects of their safety performance such as impact sensitivity. In order to reveal the crystal morphology of ammonium dinitramide/pyrazine-1,4-dioxide (ADN/PDO) cocrystal at different temperatures, the modified attachment energy model (MAE) was used at 298, 303, 308, and 313 K to predict the morphology of the ADN/PDO cocrystal under vacuum and ethanol. The results showed that under vacuum conditions, five growth planes of the ADN/PDO cocrystal were given, which were (1 0 0), (0 1 1), (1 1 0), (1 1 -1), and (2 0 -2). Among them, the ratios of the (1 0 0) and (0 1 1) planes were 40.744% and 26.208%, respectively. In the (0 1 1) crystal plane, the value of S was 1.513. The (0 1 1) crystal plane was more conducive to the adsorption of ethanol molecules. The order of binding energy between the ADN/PDO cocrystal and ethanol solvent was (0 1 1) > (1 1 -1) > (2 0 -2) > (1 1 0) > (1 0 0). The radial distribution function analysis revealed that there were hydrogen bonds between the ethanol and the ADN cations, van der Waals interactions with the ADN anions. As the temperature increased, the aspect ratio of the ADN/PDO cocrystal was reduced, making the crystal more spherical, which helped to further reduce the sensitivity of this explosive.

Research on Integrated Parallel Reactions for the High Throughput Preparation Energetic Materials

The high-throughput automatic sample addition platform technology was applied to the large-scale sample addition, pretreatment, and high-throughput synthesis of simple compounds in many fields. With the introduction of material genome technology into the field of high energy energetic materials (HEDMs), the energetic materials genome (EMG) project is implemented. Completing different reaction types at the same time has become key to high-throughput synthesis of energetic materials. In this study, three common synthetic methods (nitration, oxidation and ion exchange reactions) were selected and successfully integrated on the high-throughput automatic sample addition platform. The parallel reactions could be used for preparing energetic materials. The method is viable for high-throughput synthesis of HEDMs. The method improves the efficiency, safety, labor costs compared to conventional methods, which is of great significance for accelerating the synthesis of HEDMs.

A design of laser pyrotechnic device based on fiber laser detonation

In order to meet the application requirements of high performance, high safety and high reliability of laser explosives in future weapons and equipment, this paper tries to solve the problem of interaction reliability between laser and energetic materials, and studies the interaction law between fiber laser and energetic materials with high beam quality. The principle prototype of all-fiber laser ignition with high beam quality is developed. The interaction between high beam quality pulsed laser and energetic materials was studied. Fast and efficient ignition of pulsed fiber laser based on high beam quality is realized. Compared with semiconductor laser, the output brightness of fiber laser is high and the light energy is concentrated under the condition of the same output power, which is conducive to the instantaneous generation of high temperature hot spot when interacting with the agent, which can effectively improve the ignition efficiency. And the photoelectric conversion efficiency is high, can effectively reduce the energy supply. It is an ideal pyrotechnic device which can improve the safety of weapons and equipment in modern war.

Theoretical insights into the synthesis reaction mechanism of HMX based on TAT nitration reaction

Improving the yield and reducing the production cost of high energy density energetic material 1,3,5,7-tetranitro-1,3,5,7-tetrazacyclooctane (HMX) has been a problem for the past few decades. The synthesis of HMX by multi-step nitration of 1,3,5,7-tetraacyl-1,3,5,7-tetrazacyclooctane (TAT) is an efficient synthetic strategy, which has the advantages of mild reaction and high product recovery. However, there is a lack of sufficient theoretical research on the difficulty of TAT nitration and the difference in nitration rate at each step. To address these issues, the mechanism of TAT nitration to synthesize HMX was investigated by the density functional theory (DFT) calculations in this work. The combination of nitroxyl cation with the oxygen atom on the acetyl group hinders the nitration of the nitrogen atom on the ring skeleton. The second step of nitration of the nitrogen atom tends to occur in the para position. The rate difference between the nitration steps is determined by the driving force of the reverse reaction of the unstable intermediate and the energy barrier of the forward reaction of the stable intermediate. Through this work, the synthesis mechanism of HMX from TAT could be known more clearly.

In silico Genotoxicity Prediction by Similarity Search and Machine Learning Algorithm: Optimization and Validation of the Method for High Energetic Materials

AbstractThe European regulation REACh (Registration, Evaluation, Authorization, and restriction of Chemicals) has placed responsibility on the industry to manage the risk from chemicals since 2006. In order to ensure a high level of protection of human health and environment, toxicity prediction methods are now a widely used tool for regulatory decision making and selection of leads in new substances design. These in silico methods are an alternative to traditional in vitro and in vivo testing methods, which are laborious, time‐consuming, highly expensive, and even involve animal welfare issues. Many computational methods have been employed to predict the toxicity profile of substances, but they are mostly adapted to pharmaceutical molecules and not to High Energetic Materials (HEMs).In line with these restrictions, ArianeGroup set up a collaborative project with the French CNRS to develop optimized tools for the prediction of HEM properties, such as genotoxicity. Several in silico methods can be used to predict the properties of molecules, such as QSAR, Local QSAR or Machine Learning. We already demonstrated that using Local QSAR allows for better predictions with a good reliability [1].We therefore developed a genotoxicity prediction tool based on the structural similarity search coupled with a supervised machine learning algorithm. This tool is composed of 3 predictive models: the Ames test, the Chromosomal Aberration test and the Mouse Lymphoma Assay. The aim of this paper is to evaluate the performance of these models to predict the genotoxicity of HEMs. We also present the methodology we applied to build these models and to optimize their performances. The dimensional reduction of the training set and the hyperparameters tuning of the different algorithms showed a performance acceleration and a significant reduction of the overfitting, which caused a decline in the generalization capacity of the predictive models. The performance of the predictive models was evaluated on a test set of HEMs and compared to the results of other prediction softwares.

Insensitive High-Energy Density Materials Based on Azazole-Rich Rings: 1,2,4-Triazole N-Oxide Derivatives Containing Isomerized Nitro and Amino Groups.

It is an arduous and meaningful challenge to design and develop new energetic materials with lower sensitivity and higher energy. How to skillfully combine the characteristics of low sensitivity and high energy is the key problem in designing new insensitive high-energy materials. Taking a triazole ring as a framework, a strategy of N-oxide derivatives containing isomerized nitro and amino groups was proposed to answer this question. Based on this strategy, some 1,2,4-triazole N-oxide derivatives (NATNOs) were designed and explored. The electronic structure calculation showed that the stable existence of these triazole derivatives was due to the intramolecular hydrogen bond and other interactions. The impact sensitivity and the dissociation enthalpy of trigger bonds directly indicated that some compounds could exist stably. The crystal densities of all NATNOs were larger than 1.80 g/cm3, which met the requirement of high-energetic materials for crystal density. Some NATNOs (9748 m/s for NATNO, 9841 m/s for NATNO-1, 9818 m/s for NATNO-2, 9906 m/s for NATNO-3, and 9592 m/s for NATNO-4) were potential high detonation velocity energy materials. These study results not only indicate that the NATNOs have relatively stable properties and excellent detonation properties but also prove that the strategy of nitro amino position isomerization coupled with N-oxide is an effective means to develop new energetic materials.

Cupric coordination compounds with multiple anions: a promising strategy for the regulation of energetic materials.

To seek new high energetic materials, N-methylene-C-bridged nitrogen-rich heterocycle 1-((4,5-diamino-4H-1,2,4-triazol-3-yl)methyl)-1H-1,2,4-triazol-3,5-diamine (DATMTDA) (2) was first synthesized, and two copper coordination compounds ([Cu12(OH)4(ClO4)4(H2O)4(DATMTDA)12](ClO4)16·12H2O (3) and [Cu3(OH)(ClO4)(DATMTDA)3](ClO4)3(NO3) (4)) based on 2 were formed by introducing different anions. These compounds were characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction analysis. The crystal structures of compounds 3 and 4 are similar and crystallize in monoclinic systems with the P21/c space group, while the central copper atoms show different coordination behaviors. However, the structure of compounds 3 and 4 is analogous to a three dimensional structure owing to the O atom of OH-, forming coordinate bonds with three copper cations. The NBO charge of 2 was calculated using density functional theory to understand its coordination modes. The Hirshfeld surface calculation reveals that 3 and 4 have strong intermolecular interactions. The thermal decomposition processes, non-isothermal kinetics, and enthalpies of formation and sensitivities of these compounds were investigated. By introducing one NO3- of compound 4 to replace one ClO4- in compound 3, compound 4 shows lower density and lower decomposition peak temperature but lower sensitivity and a higher formation enthalpy than compound 3. The complex 4 possesses an outstanding catalytic effect for the decomposition of AP than that of complex 3. The results illustrate the possibility of introducing various anions into energetic coordination compounds for the regulation of energetic materials.