An Ag(i) energetic metal–organic framework assembled with the energetic combination of furazan and tetrazole: synthesis, structure and energetic performance
Abstract:A novel Ag(I) energetic MOF [Ag16(BTFOF)9]n·[2(NH4)]n () assembled with Ag(iI ions and a furazan derivative, 4,4'-oxybis[3,3'-(1H-5-tetrazol)]furazan (H2BTFOF) was successfully synthesized and structurally characterized, featuring a three-dimensional porous structure incorporating ammonium cations. The thermal stability and energetic properties were determined, revealing that the 3D energetic MOF had an outstanding insensitivity (IS > 40 J), an ultrahigh detonation pressure (P) of 65.29 GPa and a detonation ve… Show more
“…It crystallizes in the monoclinic space group P 2 1 /c with a calculated density of 3.2 g/cm 3 at 123 K (Supplementary Tables 2–6). The density value is the highest crystal density reported so far for any cyclo -N 5 ˉ complex 15 , and is largely due to the presence of four heavy silver atoms. As depicted in the Oak Ridge Thermal Ellipsoid plot (ORTEP) of [Ag(NH 3 ) 2 ] + [Ag 3 (N 5 ) 4 ]ˉ (Fig.…”
The pentazolate anion, as a polynitrogen species, holds great promise as a high-energy density material for explosive or propulsion applications. Designing pentazole complexes that contain minimal non-energetic components is desirable in order to increase the material’s energy density. Here, we report a solvent-free pentazolate complex, AgN5, and a 3D energetic-framework, [Ag(NH3)2]+[Ag3(N5)4]ˉ, constructed from silver and cyclo-N5ˉ. The complexes are stable up to 90 °C and only Ag and N2 are observed as the final decomposition products. Efforts to isolate pure AgN5 were unsuccessful due to partial photolytical and/or thermal-decomposition to AgN3. Convincing evidence for the formation of AgN5 as the original reaction product is presented. The isolation of a cyclo-N5ˉ complex, devoid of stabilizing molecules and ions, such as H2O, H3O+, and NH4+, constitutes a major advance in pentazole chemistry.
“…It crystallizes in the monoclinic space group P 2 1 /c with a calculated density of 3.2 g/cm 3 at 123 K (Supplementary Tables 2–6). The density value is the highest crystal density reported so far for any cyclo -N 5 ˉ complex 15 , and is largely due to the presence of four heavy silver atoms. As depicted in the Oak Ridge Thermal Ellipsoid plot (ORTEP) of [Ag(NH 3 ) 2 ] + [Ag 3 (N 5 ) 4 ]ˉ (Fig.…”
The pentazolate anion, as a polynitrogen species, holds great promise as a high-energy density material for explosive or propulsion applications. Designing pentazole complexes that contain minimal non-energetic components is desirable in order to increase the material’s energy density. Here, we report a solvent-free pentazolate complex, AgN5, and a 3D energetic-framework, [Ag(NH3)2]+[Ag3(N5)4]ˉ, constructed from silver and cyclo-N5ˉ. The complexes are stable up to 90 °C and only Ag and N2 are observed as the final decomposition products. Efforts to isolate pure AgN5 were unsuccessful due to partial photolytical and/or thermal-decomposition to AgN3. Convincing evidence for the formation of AgN5 as the original reaction product is presented. The isolation of a cyclo-N5ˉ complex, devoid of stabilizing molecules and ions, such as H2O, H3O+, and NH4+, constitutes a major advance in pentazole chemistry.
“…Meanwhile, the self‐accelerating decomposition temperature ( T SADT ) and critical temperature of thermal explosion ( T b ), which are two important parameters to ensure safe storage and process operations, are also calculated (Table S2 in the Supporting Information). The six compounds show preferable thermal stability in the exothermic decomposition stage, in which the T SADT and T b of 6 are, respectively, 379.0 and 384.6 °C, exceeding common explosives like FOX‐7 (206.0 and 207.1 °C) and one of the most powerful IH‐ECPs, [Ag 16 (BTFOF) 9 ] n ⋅ [2(NH 4 )] n (228.2 and 241.2 °C) …”
Section: Resultsmentioning
confidence: 99%
“…[37,38] However,i deal insensitive high-energetic coordination polymers (IH-ECPs) conforming to the concept of IHEs with outstanding insensitivity (IS > 40 J, FS > 360 N) and detonation velocity( D > 9kms À1 )a re rare in the published literature. [39][40][41][42][43][44][45][46][47] To date, only two high-performance IH-ECPsh ave been constructed based on tetrazole derivatives:4 ,4'oxybis(3,3'-(1 H-5-tetrazol))furazan [46] and bis(tetrazole)methane. [47] As the primary energy source, these nitrogen-rich compounds not only have abundant inherent energetic bonds between atoms of C/N and N/N, but also will bring diversec oordination structures through high nitrogen aromatic moieties.…”
Constructing insensitive high-performance energetic coordination polymers (ECPs) with alkali/alkali-earth metal ions and a nitrogen-rich organic backbone has been proved to be a feasible strategy in this work. Six diverse dimensional novel ECPs (compounds 1-6) were successfully synthesized from Na , Cs , Ca , Sr , Ba ions and a nitrogen-rich triheterocyclic 4,5-bis(tetrazol-5-yl)-2 H-1,2,3-triazole (H BTT). All compounds show outstanding stability and low sensitivity, the thermal stability of these ECPs are significantly improved as the structural reinforcement increases from 1D to 3D, in which the decomposition temperature of 3D Ba based compound 6 is as high as 397 °C. Long-term storage experiments show that compounds 5 and 6 are stable enough at high temperature. Moreover, the six compounds hold considerable detonation performances, in which Ca based compound 5 possesses the detonation velocity of 9.12 km s , along with the detonation pressure of 34.51 GPa, exceeding those of most energetic coordination polymers. Burn tests further certify that the six compounds can be versatile pyrotechnics.
“…Many investigators have recently demonstrated the possibility of using nitrogen-rich MOFs as high explosives [25,26,27,28,29,30,31,32,33,34,35,36,37,38,39,40,41,42,43,44,45,46,47,48]. MOFs consist of metal ions (Pb 2+ , Ag + , etc.…”
Section: Introductionmentioning
confidence: 99%
“…The sensitivities of these 3D MOFs are significantly lower than those of reported energetic coordination polymers, such as 1D (CHP, IS = 0.5 J) and 2D (ZnHHP, IS = 2.5 J; CHHP, IS = 0.8 J) MOFs. An increasing number of investigations on E-MOFs as new-generation high explosives were reported by Chen et al [32,33,36,38,39,40,42,44,45,50,51], Pang et al [28,48,52], Shreeve et al [49,53], and so on [41,47,54,55,56] because of the advantages of 3D MOFs.…”
The focus of energetic materials is on searching for a high-energy, high-density, insensitive material. Previous investigations have shown that 3D energetic metal–organic frameworks (E-MOFs) have great potential and advantages in this field. A nitrogen-rich E-MOF, Pb(bta)·2H2O [N% = 31.98%, H2bta = N,N-Bis(1H-tetrazole-5-yl)-amine], was prepared through a one-step hydrothermal reaction in this study. Its crystal structure was determined through single-crystal X-ray diffraction, Fourier transform infrared spectroscopy, and elemental analysis. The complex has high heat denotation (16.142 kJ·cm−3), high density (3.250 g·cm−3), and good thermostability (Tdec = 614.9 K, 5 K·min−1). The detonation pressure and velocity obtained through theoretical calculations were 43.47 GPa and 8.963 km·s−1, respectively. The sensitivity test showed that the complex is an impact-insensitive material (IS > 40 J). The thermal decomposition process and kinetic parameters of the complex were also investigated through thermogravimetry and differential scanning calorimetry. Non-isothermal kinetic parameters were calculated through the methods of Kissinger and Ozawa-Doyle. Results highlighted the nitrogen-rich MOF as a potential energetic material.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.