Three new energetic complexes, [Pb(bta)(H2O)]n (1), [PbCu(bta)2(H2O)5]·2H2O (2) and PbCu(bta)2 (3) (H2bta = N,N-bis(1H-tetrazole-5-yl)-amine), have been synthesized and characterised. In particular, 3 was readily synthesized by dehydration of 2 at 190 °C. Single crystal X-ray diffraction revealed that 1 has a 3D framework structure and 2 presents a 3D supermolecular architecture. Thermoanalyses demonstrated that the main frames of 1 and 2 have good thermostabilities up to 314 °C for 1 and 231 °C for 2. Non-isothermal kinetic and thermodynamic parameters of exothermic decomposition processes of 1 and 2 were obtained by Kissinger's and Ozawa's methods. Based on the constant-volume combustion energies measured by a precise rotating-bomb calorimeter, the standard molar enthalpies of formation of 1 and 2 were determined. The calculation of the detonation properties of 1 and 2 and the impact sensitivity tests of 1, 2 and 3 were carried out. In addition, 1, 2 and 3 were explored as combustion promoters to accelerate the thermal decompositions of RDX (1,3,5-trinitro-1,3,5-triazine) by differential scanning calorimetry. Experimental results showed that 1, 2 and 3 can be used as HEDMs in the field of combustion promoters and insensitive 2 can be regarded as a safer form for mass storage and transportation than sensitive 3.

A new 1D CuII coordination polymer, formulated as {[Cu(TZA)(PNA)]·H2O}n (1) (HTZA = tetrazole-1-acetic acid, HPNA = p-nitrobenzoic acid), was synthesized and structurally characterized. Thermogravimetric analysis demonstrated that the main frame of 1 exhibited good thermostability up to 473 K. The non-isothermal kinetics for the first exothermic process of 1 were studied by Kissinger and Ozawa methods. The magnetic study revealed that 1 possessed antiferromagnetic exchange interactions between CuII ions through the carboxyl-bridge. The low-temperature (1.9 to 300 K) heat capacity of 1 was measured using the heat-capacity option of a Quantum Design Physical Property Measurement System (PPMS). In addition, the thermodynamic functions in the experimental temperature range were derived by fitting the heat-capacity data to a series of theoretical and empirical models. The standard entropy and standard enthalpy of 1 were respectively calculated to be 411.37 ± 4.11 J mol−1 K−1 and 60.21 ± 0.60 kJ mol−1.

Three-dimensional MOFs, {[Cu3(tz)4Cl2] 2CH3OH}n (Htz = 1H-1,2,3,4-tetrazole), have been synthesized in methanol. It was characterized by chemical analysis, element analysis, IR spectroscopy, single-crystal X-ray diffraction and thermal analysis. Thermogravimetric analysis demonstrated that the MOFs after removing methanol molecules possessed good thermostability with decomposition temperature up to 533 K. The enthalpy change of liquid-phase formation reaction was determined by a RD496–2000 microcalorimeter at 298.15 K with the value of (−46.63 ± 0.26) kJ mol−1. The enthalpy change of solid-phase formation reaction was calculated as (−573.89 ± 0.89) kJ mol−1 on the basis of a designed thermochemical cycle. The thermodynamics of formation reaction of the MOFs was investigated by changing the temperature of liquid-phase reaction. Based on the experimental results, fundamental kinetic and thermodynamic parameters k, n, E, \(\Delta H_{ \ne }^{\theta }\), \(\Delta S_{ \ne }^{\theta }\) and \(\Delta G_{ \ne }^{\theta }\) were obtained. The specific heat capacity at 298.15 K was determined to be (1.87 ± 0.08) J K−1 g−1 by a RD496-2000 calorimeter. In addition, the constant volume combustion energy of title MOFs was determined by a RBC-II rotating-bomb calorimeter at 298.15 K. The standard molar enthalpy of combustion and standard molar enthalpy of formation were calculated to be (−4736.43 ± 4.03) kJ mol−1 and (293.42 ± 4.11) kJ mol−1, respectively.

The design and synthesis of explosives with high performance, good thermal stability, and low sensitivity is an important subject for the development of energetic materials. Energetic complexes have recently emerged as a promising energetic material form. As one of the representatives, [Cu(Htztr)2(H2O)2]n (H2tztr = 3-(1H-tetrazol-5-yl)-1H-triazole) was previously reported with good energetic performance, outstanding thermostability (Tdec = 345 °C) and low sensitivity to impact and friction stimuli. However, due to the existence of water molecules, its effective energy density is remarkably decreased, resulting in a diminished detonation performance. In order to further improve the detonation performance, using [Cu(Htztr)2(H2O)2]n as a precursor, {[Cu(Htztr)(H2O)]NO3}n (1) and [Cu(H2tztr)2(HCOO)2]n (2) were synthesized by the axial substitution reaction with NO3− and HCOO−. The structures of 1 and 2 were characterized by single crystal X-ray diffraction. Both of them exhibit high thermal stabilities and insensitivities to impact and friction. Moreover, the same DFT calculation methodology shows that the heat of detonation of 2 (3.5663 kcal g−1) is significantly higher than that of the precursor [Cu(Htztr)2(H2O)2]n (2.1281 kcal g−1). Meanwhile, the empirical Kamlet–Jacobs equations were used to theoretically predict the detonation properties of the title complexes, and the results show that 1 and 2 have excellent detonation velocity (D) and detonation pressure (P).

•An energetic MOFs with dinuclear nickel unit has been synthesized and characterized.•The Arrhenius equation, derived from kinetics analysis, is ln k = 55.89 − 332.01 × 103/RT.•The standard molar enthalpy of formation of the compound is determined by a thermochemical cycle.•The molar heat capacity at T = 298.15 K is determined to be 1.42 ± 0.11 J · K−1 · g−1.A new energetic MOFs, {[Ni2(C2H5N5)2(C3H2O4)2(H2O)]·3H2O}n (Hdatrz (C2H5N5) = 3,5-diamino-1,2,4-triazole, H2mal (C3H4O4) = malonic acid), has been synthesized and characterized by element analysis, chemical analysis, IR spectroscopy, single-crystal X-ray diffraction and thermal analysis. X-ray diffraction analysis confirmed that the compound featured a 2D layer structure with dinuclear Ni(II) unit. Thermal analysis demonstrated that the compound after dehydration have good thermostability with decomposition temperature up to 633 K. The non-isothermal kinetics for the compound was studied by Kissinger’s and Ozawa’s methods. The Arrhenius equation of initial thermal decomposition process of compound can be expressed as ln k = 55.89 − 332.01 × 103/RT. Furthermore, a reasonable thermochemical cycle was designed based on the preparation reaction of the compound, and standard molar enthalpy of dissolution of reactants and products were measured by RD496-2000 calorimeter. Finally, the standard molar enthalpy of formation of the compound was determined to be −(2766.3 ± 2.3) kJ · mol−1 in accordance with Hess’s law. In addition, the specific heat capacity of the compound at T = 298.15 K was determined to be 1.42 ± 0.11 J · K−1 · g−1 by RD496-2000 calorimeter.

A new 1D CuII coordination polymer, formulated as {[Cu(TZA)(PNA)]·H2O}n (1) (HTZA = tetrazole-1-acetic acid, HPNA = p-nitrobenzoic acid), was synthesized and structurally characterized. Thermogravimetric analysis demonstrated that the main frame of 1 exhibited good thermostability up to 473 K. The non-isothermal kinetics for the first exothermic process of 1 were studied by Kissinger and Ozawa methods. The magnetic study revealed that 1 possessed antiferromagnetic exchange interactions between CuII ions through the carboxyl-bridge. The low-temperature (1.9 to 300 K) heat capacity of 1 was measured using the heat-capacity option of a Quantum Design Physical Property Measurement System (PPMS). In addition, the thermodynamic functions in the experimental temperature range were derived by fitting the heat-capacity data to a series of theoretical and empirical models. The standard entropy and standard enthalpy of 1 were respectively calculated to be 411.37 ± 4.11 J mol−1 K−1 and 60.21 ± 0.60 kJ mol−1.

Three new energetic complexes, [Pb(bta)(H2O)]n (1), [PbCu(bta)2(H2O)5]·2H2O (2) and PbCu(bta)2 (3) (H2bta = N,N-bis(1H-tetrazole-5-yl)-amine), have been synthesized and characterised. In particular, 3 was readily synthesized by dehydration of 2 at 190 °C. Single crystal X-ray diffraction revealed that 1 has a 3D framework structure and 2 presents a 3D supermolecular architecture. Thermoanalyses demonstrated that the main frames of 1 and 2 have good thermostabilities up to 314 °C for 1 and 231 °C for 2. Non-isothermal kinetic and thermodynamic parameters of exothermic decomposition processes of 1 and 2 were obtained by Kissinger's and Ozawa's methods. Based on the constant-volume combustion energies measured by a precise rotating-bomb calorimeter, the standard molar enthalpies of formation of 1 and 2 were determined. The calculation of the detonation properties of 1 and 2 and the impact sensitivity tests of 1, 2 and 3 were carried out. In addition, 1, 2 and 3 were explored as combustion promoters to accelerate the thermal decompositions of RDX (1,3,5-trinitro-1,3,5-triazine) by differential scanning calorimetry. Experimental results showed that 1, 2 and 3 can be used as HEDMs in the field of combustion promoters and insensitive 2 can be regarded as a safer form for mass storage and transportation than sensitive 3.