Polynitro-Functionalized Triazolylfurazanate Triaminoguanidine

Jun 19, 2019 - Di(triaminoguanidinium) 3-nitramino-4-(3-(dinitromethanidyl)-1,2 ... (1−5) It is generally accepted that primary explosives upon igni...
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Polynitro-Functionalized Triazolylfurazanate Triaminoguanidine: Novel Green Primary Explosive with Insensitive Nature Jinchao Ma, Jie Tang, Hongwei Yang,* Zhenxin Yi, Ganggang Wu, Shunguan Zhu, Wenchao Zhang, Yanchun Li, and Guangbin Cheng* School of Chemical Engineering, Nanjing University of Science & Technology, Nanjing 210094, China

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S Supporting Information *

ABSTRACT: Exploring a green and safe primary explosive to replace very toxic and sensitive lead azide and lead styphnate takes great efforts. Here, a series of polynitro-functionalized triazolylfurazanate energetic materials have been reported. These new compounds were fully characterized by infrared, multinuclear NMR spectra, mass spectra, elemental analysis, and differential scanning calorimetry measurements. The structure of mono-diaminoguanidinium salt (17) was determined by single-crystal X-ray diffraction. Inspired by the high pressurization rate and fast energy release in triaminoguanidinium salts, some suitability evaluation for primary explosives has been applied. Di(triaminoguanidinium) 3-nitramino-4-(3-(dinitromethanidyl)-1,2,4-triazol5-yl)furazanate exhibits an excellent gas-generating capability (Pmax = 9.03 Mpa) and combustion performance (dP/dtmax = 201.5 GPa s−1) close to fast thermite Al/CuO (Pmax = 8.49 Mpa, dP/dtmax = 252.2 GPa s−1). Moreover, the good initiation capacity (60 mg for 500 mg RDX) coupled with insensitivity in this compound (IS = 17.4 J, FS = 240 N, ESD > 0.225 J) make it a promising green and insensitive primary explosive. KEYWORDS: heterocyclic chemistry, energetic material, insensitive primary explosive, combustion experiment, triaminoguanidinium salt

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INTRODUCTION Primary explosive plays a very important role in the area of energetic materials because of their capability to ignite propellants and secondary explosives.1−5 It is generally accepted that primary explosives upon ignition undergo a rapid deflagration-to-detonation transition process and further generate enhanced power (a large amount of heat, gas, or shockwave) to a less sensitive secondary explosive.6 The most known and commonly used primary explosives are the two lead-based salts, i.e., lead azide (LA) and lead styphnate (LS).7,8 Problematically, due to the high toxicity of the heavy metal contained in LA and LS, environmental and human health are greatly threatened by their wide use in civilian and military operations. In addition, sensitivity of the current leadbased systems (LA, IS = 2.5−4 J, FS = 0.1−1 N, ESD < 5 mJ; LS, IS = 2.25 J, FS = 1.45 N, ESD = 0.14 mJ) brings out a lot of unnecessary casualties,9 which make the application of LA and LS a contradiction between controllable trigger and unexpected accident. So how to develop green and insensitive alternatives to LA and LS was a major current focus in the energetics community. In recent years, several promising potassium-based energetic materials for green primary explosives have been researched (Scheme 1). For example, potassium 1,1′-dinitramino-5,5′bistetrazolate (K2DNABT) and 1,5-di(nitramino)tetrazolate (K2DNAT),10,11 which consist of unstable structures of 1nitramino-tetrazole and “green” metal potassium, are very sensitive to impact and friction (K2DNABT, IS = 1 J, FS ≤ 1 © XXXX American Chemical Society

N, ESD = 3 mJ; K2DNAT, IS = 1 J, FS < 5 N). Detonation test revealed that K2DNABT and K2DNAT are suitable as ingredients of primary explosive. Furthermore, potassium 4,5bis(dinitromethyl)furoxanate (K2BDNMF) and potassium 4,4′-bis(dinitromethyl)-3,3′-azofurazanate (K2BDNAF) with high sensitivity (K2BDNMF, IS = 2 J, FS = 5 N; K2BDNAF, IS = 2 J, FS = 20 N) and remarkable detonation performance (K2BDNMF, vD = 7759 m s−1, P = 27.3 GPa; K2BDNAF, vD = 8138 m s−1, P = 30.1 GPa)12,13 are believed to be competitive candidates as green primary explosive. However, the issue of high sensitivity in primary explosives, which can directly make casualties in case of premature or accidental explosions, still exists. In our previous work, a metal-free polyazido compound 3,6bis(2-(4,6-diazido-1,3,5-triazin-2-yl)-hydrazinyl)-1,2,4,5-tetrazine (BDTHT) with a relatively low sensitivity (IS = 7.4 J, FS = 35.3 N, ESD = 205 mJ) was reported as an environmentalfriendly candidate to replace LA.14 With the unremitting effort to pursue metal-free and insensitive primary explosives, a series of polynitro-triazolylfurazanate compounds were synthesized in this work. Among them, di(triaminoguanidinium) 3-nitramino4-(3-(dinitromethanidyl)-1,2,4-triazol-5-yl)furazanate (DNDTF), which consists only of C, H, N, and O, with excellent gas-generating capability and fast combustion Received: May 28, 2019 Accepted: June 19, 2019 Published: June 19, 2019 A

DOI: 10.1021/acsami.9b08363 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX

Research Article

ACS Applied Materials & Interfaces

nidinium salt used as an insensitive primary explosive with sensitivities compatible to those of the insensitive secondary explosive trinitrotoluene (TNT). Moreover, this novel strategy of using polynitro-functionalized triazolylfurazanate triaminoguanidine as a primary explosive may open the door for a new green and insensitive primary explosive.

Scheme 1. Progress Research on Primary Explosive

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RESULTS AND DISCUSSION Synthesis. As is shown in Scheme 2, the synthesis of intermediate compounds 2-(5-(4-amino-1,2,5-oxadiazol-3-yl)1,2,4-triazol-3-yl)acetic acid (2) and ethyl 2-(5-(3-amino-1,2,5oxadiazol-4-yl)-1,2,4-triazol-3-yl)acetate (3) starts from 3carbohydrazide-4-aminofurazan,15 which is first treated with ethyl 3-ethoxy-3-iminopropionate16 to give ethyl 3-(2-(4amino-1,2,5-oxadiazole-3-carbonyl)hydrazinyl)-3-iminopropanoate (1, yield: 85%). Compound 1 is reacted with sodium hydroxide solution and glacial acetic acid to yield 2 (71%) and 3 (93%), respectively. Besides, compound 3 can also be obtained from 2 through esterification reaction (yield: 89%). Compound 2 was nitrated using mixed nitric acid and sulfuric acid as the reaction medium at 25 °C to give 3-nitramino-4-(3(trinitromethyl)-1,2,4-triazol-5-yl)furazan (4, yield: 83%). The energetic salts 5 and 6 (yield: 83, 80%) were directly obtained by acid−base reactions with 4 and energetic bases. Salts 7−10 (81−82%) were prepared through two-step route using silver salt as the intermediate. However, gem-dinitro compound 12− 14 (75−78%) were given by treating compound 4 with ammonia, hydrazine, and hydroxylamine, respectively. The nitration of 3 was realized with nitric acid and sulfuric acid to obtain compound 11 as a white solid, which slowly converted into light yellow oil with increase in temperature. Therefore, 11 was treated immediately with bases in ethanol, which led to the precipitation of salts 12−14 (yield: 83−89%). The neutral compound 15 (yield: 83%) was obtained by acidifying 12 with hydrochloric acid. Mono-guanidinium salts 16, 17, and 18

reaction, has been proved to qualify as a primary explosive. To the best of our knowledge, DNDTF is the first triaminogua-

Scheme 2. Synthesis of Polynitro-functionalized Triazolylfurazan and Their Energetic Salts

B

DOI: 10.1021/acsami.9b08363 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX

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ACS Applied Materials & Interfaces

Compound 17·3H2O crystallizes in the monoclinic C2/c space group with four molecules in the unit cell and the calculated density of 1.78 g cm−3 at 100 K. Detailed crystallographic information about 17·3H2O is given in the SI. As expected, the triazole ring and the furazan ring are coplanar (Figure 1a), where all atoms connected with this ring are nearly in the same plane, which could be seen from the torsion angle of N8−C5−C4−N7 (−177.5°), N9−C5−C4− N6 (−178.0°), N1−N2−C1−C2 (−179.4°), and C1−C2− C3−N5 (179.9°). Using the nitrogen in triazole as the donor, two neighboring heterocyclic rings in the same plane were connected with each other through an intermolecular hydrogen bond of N6−H6···O2 (Figure 1b). In addition, two intermolecular hydrogen bond interactions of N10−H10···O1 and N13−H13···N3 connect heterocyclic rings with neighboring diaminoganide ions. Unit cell view along a, b, and c axes are given in the SI. Physicochemical and Energetic Properties. The thermal stabilities of the newly prepared polynitro-furazantriazole compounds were determined using differential scanning calorimetry (DSC) measurements. As shown in Table 1, 3-nitramino-4-(3-(trinitromethyl)-1,2,4-triazol-5-yl)furazanate compounds 4−10 decompose at 67−140 °C and 3nitramino-4-(3-(dinitromethanidyl)-1,2,4-triazol-5-yl)furazanate compounds 12−20 and DNDTF without trinitromethy groups are thermally stable and decompose between 91 and 214 °C. The experimental densities of compounds 4− 10, 12−20, and DNDTF are in the range of 1.73−1.89 g cm−3. All of these compounds possess high nitrogen plus oxygen content (77.9−82.1%), which are superior to those of TNT (60.79%) and comparable to those of cyclotrimethylenetrinitramine (RDX, 81.4%). The heats of formation (HOF) of 4−10, 12−20, and DNDTF were obtained using the isodesmic reaction approach using the Gaussian 09 programs (SI). With a large number of

(yield: 83−86%) and di-guanidinium salts 19, 20, and DNDTF (yield: 84−85%) were prepared through a two-step route using silver salts as the intermediate. X-ray Crystallography. Through slow evaporation of water at room temperature, crystals of 17·3H2O suitable for single-crystal X-ray diffraction were obtained. Their structures are shown in Figure 1. Selected bond lengths, bond angles, and hydrogen bonds are given in the Supporting Information (SI).

Figure 1. (a) Single-crystal X-ray structure of 17·3H2O and (b) some hydrogen bonds (dashed lines) in the crystal structure of 17·3H2O.

Table 1. Physicochemical and Energetic Properties of Compounds 4−10, 12−20, and DNDTF Comparison with TNT and RDX compd

Tdeca (°C)

ρb (g cm−3)

N + O%c

N%d

ΔHfe (kJ mol−1/kJ g−1)

V0f (L kg−1)

vDg (m s−1)

Ph (GPa)

ISi (J)

FSj (N)

4 5 6 7 8 9 10 12 13 14 15 16 17 18 19 20 DNDTF TNTk RDXl

67 120 134 112 117 120 140 155 205 178 91 214 213 185 190 180 185 295 204

1.89 1.79 1.80 1.81 1.81 1.80 1.79 1.78 1.82 1.83 1.85 1.79 1.80 1.78 1.76 1.74 1.73 1.65 1.80

82.1 79.1 79.1 80.5 80.9 81.4 81.8 79.4 80.5 81.2 79.1 78.4 79.0 79.5 77.9 78.9 79.7 60.79 81.04

40.5 45.6 45.6 44.9 46.7 48.3 49.8 46.0 49.9 42.0 41.9 48.5 50.3 51.9 53.0 55.5 57.8 18.5 37.8

549.4/1.59 662.9/1.54 779.7/1.81 375.8/0.93 562.3/1.34 578.3/1.33 685.0/1.52 157.5/0.47 505.9/1.39 296.9/0.81 537.4/1.79 747.5/1.99 762.9/1.96 870.7/2.15 539.6/1.20 596.1/1.24 829.3/1.63 −59.4/−0.26 70.3/0.32

738.0 755.9 761.3 768.5 780.3 793.8 807.7 811.4 839.9 787.9 742.2 792.2 806.3 822.5 848.2 866.2 880.7 643.8 794.0

9278 8635 8817 8665 8804 8788 8833 8557 9085 8929 9005 8862 8941 8958 8680 8667 8806 7304 8795

39.0 32.2 34.2 32.6 34.0 33.5 33.6 30.4 34.4 36.0 36.3 33.4 33.7 33.4 29.1 28.8 29.5 21.3 34.9

4.4 8.7 5.5 11.0 9.8 12.3 13.8 15.5 7.7 12.3 8.7 16.5 18.4 20.7 15.5 13.8 17.4 15 7.4

60 120 100 140 120 140 160 160 100 160 100 240 360 360 180 160 240 >353 120

Thermal decomposition temperature under nitrogen gas (DSC, 5 °C min−1). bDensity measured by gas pycnometer (25 °C). cNitrogen and oxygen. dNitrogen content. eCalculated heat of formation. fGas volume after detonation. gCalculated detonation velocity. hCalculated detonation pressure. iImpact sensitivity. jFriction sensitivity. kRef 17. lRef 18. a

C

DOI: 10.1021/acsami.9b08363 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX

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ACS Applied Materials & Interfaces N−N and N−O bonds, all new energetic compounds exhibit positive heats of formation ranging from 157.5 kJ mol−1/0.47 kJ g−1 (12) to 870.7 kJ mol−1/2.15 kJ g−1 (18). Using the calculated heats of formation and the experimental densities at room temperature, detonation properties (pressures (P) and velocities (vD)) and gas volume after detonation (V0) were calculated with EXPLO5(v6.01) program. Lying in the range of 28.8−39.0 GPa and 8557−9278 m s−1, respectively, the detonation velocities and pressures of these compounds are much better than those of TNT (vD = 6881 m s−1, P = 19.5 GPa). Even more, most of these compounds come up with the common explosive RDX (vD = 8795 m s−1, P = 34.9 GPa). As the nitrogen content increases, 3-nitramino-4-(3-(dinitromethanidyl)-1,2,4-triazol-5-yl)furazanate salts 12−20 and DNDTF show a higher gas production (742.2−880.7 L kg−1) than 3-nitramino-4-(3-(trinitromethyl)-1,2,4-triazol-5yl)furazanate compounds 4−10 (738.0−807.7 L kg−1). In addition, it is obvious that for triaminoguanidinium salt, especially DNDTF, the gas volume after detonation (880.7 L kg−1) reaches the maximum among these new compounds. For initial safety testing, the impact and friction sensitivities of 4−10, 12−20, and DNDTF was investigated. The data collected are summarized in Table 1. The impact and friction sensitivities of these compounds lie in the range of 4.4−20.7 J and 60−360 N, respectively. Among them, neutral compounds 4 and 15 and salts 5, 6, 8, and 13 are relatively sensitive to impact (IS ≤ 10 J). In contrast, compounds 12 (IS = 15.5 J), 16−19 (IS ≥ 15.5 J), and DNDTF (IS = 17.4 J) possess better impact sensitivity than TNT (IS = 15 J). In friction-sensitivity tests, except compound 4 (FS = 60 N), 6 (FS = 100 N), 13 (FS = 100 N), and 15 (FS = 100 N), all of the other compounds show preferable stability than RDX (FS = 120N). Combustion Experiment. It was believed that the high initiating capacity of primary explosives was closely related to the quantity of gaseous products of the condensed explosive released as a result of a chemical reaction.19 The constantvolume combustion experiment is widely used in thermite, primary explosive, and gas-generating agent for studying the law of pressure change when energetic materials burned under constant volume.20 A high pressure-up rate, which represents high reaction rate is preferred in primary explosive. The combustion experiment was conducted by loading 6 mg samples and 0.5 mg ignition charge (B/KNO3) into the closed explosive device (0.0126 mL), and which was ignited by heating the nickel-chromium wire (24 A electricity is introduced, duration 110 ms). The schematic diagram, setup of the experimental device, and combustion process are shown in Figure 2. The constant-volume combustion results of several new synthesized compounds, common gas-generating composition nitroguanidine (NG), and the well-known fast thermite Al/ CuO (which have been widely studied by its high initiation capacity) are shown in Table 2. Compound 6 reached a maximum pressure of 5.98 MPa after a pressure-up process of 177.6 μs, and its maximum pressure-up rate reached 147.7 GPa s−1. Diaminoguanidinium salt 9 boosts Pmax to 5.10 MPa after a delay time of 178.8 μs, for which the maximum pressure-up rates reached 84.4 GPa s−1. Triaminoguanidine salt 10, by contrast, exhibits a delay time of 68.8 μs, a maximum pressure of 7.50 MPa, and a maximum pressure-up rate of 189.4 GPa s−1. For dinitro salts 12, 13, 18, 19, and DNDTF, the delay times lie in the range of 86.1−471.6 μs, Pmax from 3.63 to 9.03 MPa, and maximum pressure-up rates from 73.7 to 201.5 GPa

Figure 2. (a) Schematic test setup. (b) The P−t relationship of 6, 9, 10, 12, 13, 15, DNDTF, nitroguanidine (NG), and Al/CuO during combustion.

Table 2. Constant-Volume Combustion Performance of 6, 9, 10, 12, 13, 15, DNDTF, NG, and Al/CuO

a

compound

Pmaxa (MPa)

tb (μs)

dP/dtmaxc (Gpa s−1)

6 9 10 12 13 18 19 DNDTF NG Al/CuO

5.98 5.10 7.50 3.63 7.60 6.81 7.39 9.03 3.12 8.49

177.6 178.8 68.8 471.6 156.8 86.11 365.6 131.2 450 111.3

147.7 84.4 189.4 73.7 184.5 122.4 120.2 201.5 22.8 252.2

Maximum pressure. bPressure rise time. cMaximum pressure-up rate.

s−1. All of these compounds show gas productivity and pressure-up rate higher than those of NG (Pmax = 3.12 Mpa, dP/dtmax = 22.8 GPa s−1). Especially, triaminoguanidine salts 10 and DNDTF possess excellent gas-generating capabilities (Pmax = 7.50, 9.03 Mpa) and combustion performance (dP/ dtmax = 189.4, 201.5 GPa s−1), which are close to those of Al/ CuO (Pmax = 8.49 Mpa, dP/dtmax = 252.2 GPa s−1). Furthermore, to gain insight into the burning properties of triaminoguanidine salts directly, high-speed videos have been used to record the combustion process of 10 and DNDTF. The combustion of 10 and DNDTF on nickel-chromium wire under fast heating is shown in Figure 3a,b, respectively. It is obvious from the images that DNDTF (Figure 3b) shows a more violent reaction than 10 (Figure 3a). The ignition delay time and the total burning time for compound 10 were 19 and 221 ms, respectively, while those for DNDTF were 2 and 182 ms, respectively. These results suggest much faster energy release and pressurization rate for DNDTF. D

DOI: 10.1021/acsami.9b08363 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX

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ACS Applied Materials & Interfaces

Figure 3. Selected images for compound 10 (a) and DNDTF (b) recorded by a high-speed camera.

(BDTHT, Φ = 20 mm) we earlier reported were also tested for comparison. Furthermore, as DNDTF shows comparable calculated detonation performance to RDX (vD = 8795 m s−1, P = 34.9 GPa), some detonation tests were performed in which DNDTF was used as the secondary explosive; the results show its versatility as both primary and second explosives. Sixty milligrams of LS detonated 500 mg of DNDTF, bringing the diameter of the lead plate crater to Φ = 16 mm. In addition, without any primes, DNDTF can be detonated (Φ = 12 mm) directly with the nonel. The physical properties of DNDTF and some of the reported primary explosives are summarized in Table 3. DNDTF has good thermal stability, with an onset decomposition temperature of 185 °C. It is very remarkable that DNDTF was found to be far less sensitive (IS = 17.4 J, FS = 240 N, ESD > 0.225 J) than the commonly used primary explosive (LA, IS = 2.5−4 J, FS = 0.1−1 N, ESD < 5 mJ; LS, IS = 2.2 J, FS = 1.45 N, ESD = 0.14 mJ) and the relatively insensitive BDTHT we reported earlier (IS = 7.4 J, FS = 35.3 N, ESD = 0.205 J). In addition, the calculated detonation velocity of DNDTF is 8806 m s−1, which is superior than that of BDTHT (8365 m s−1) and much higher than that of LA (5920 m s−1) and LS (5600 m s−1).

Detonation Tests. DNDTF shows preferable properties to primary explosive (excellent press-up rate dP/dtmax = 201.5 GPa s−1, fast combustion reaction tdel = 2 ms, ttol = 182 ms). To determine the feasibility as a primary explosive, several detonation tests were carried out. This detonation experiment against a 5 mm lead block was performed using 60 mg of primary explosives to detonate 500 mg of second explosives with a plastic nonel (Figure 4).14,21 As expected, the energy produced using 60 mg of DNDTF as a primary explosive was easily strong enough to detonate 500 mg of RDX (Φ = 20 mm). Under the same experimental conditions, two commonly used primary explosives (LA, Φ = 21 mm; LS, Φ = 20 mm) and the metal-free primary explosive

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CONCLUSIONS A series of polynitro-functionalized triazolylfurazanate and their salts have been synthesized and characterized. Di(triaminoguanidinium) 3-nitramino-4-(3-(dinitromethanidyl)1,2,4-triazol-5-yl)furazanate (DNDTF) with excellent gasgenerating capability (cp. DNDTF, Pmax = 9.03 Mpa and NG, Pmax = 3.12 Mpa), high pressure-up rate (cp. DNDTF, dP/dtmax = 201.5 GPa s−1 and Al/CuO, dP/dtmax = 252.2 GPa s−1), and a fast combustion reaction (tdel = 2 ms, ttol = 182 ms) has been proved to qualify as a primary explosive. The detonation experiment demonstrated that DNDTF (Φ = 20 mm) has excellent ignition ability, which is comparable to that of LA (Φ = 21 mm), LS (Φ = 20 mm), and BDTHT (Φ = 20 mm). In addition, DNDTF exhibits good stability to impact (IS = 17.4 J), friction (FS = 240 N), and electricity (ESD > 0.225 J). Considering its good ignition ability, absence of metal, and insensitive nature, DNDTF shows promising potential as a green and insensitive primary explosive. More interestingly, through the exploration of polynitro-functionalized heterocyclic triaminoguanidine salt used as primary explosive, there is a new inspiration to upgrade the defective lead-based primary explosives.

Figure 4. (a) Schematic test setup. (b) Setup of the detonation test. (c)−(h) Perforated lead plate as the result of detonation tests: (c) 60 mg of LA and 500 mg of RDX; (d) 60 mg of LS and 500 mg of RDX; (e) 60 mg of BDTHT and 500 mg of RDX; (f) 60 mg of DNDTF and 500 mg of RDX; (g) 60 mg of LA and 500 mg of DNDTF; and (h) 560 mg of DNDTF. E

DOI: 10.1021/acsami.9b08363 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX

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ACS Applied Materials & Interfaces Table 3. Energetic Performance Parameters of LA, LS, BDTHT, and DNDTF LAn

LSo

BDTHTq

DNDTF

formula M (g mol−1) ISa (J) FSb (N) ESDc (mJ) Nd (%) ΩCOe (%) ΩCO2f (%)

PbN6 291.2 2.5−4 0.1−1 225 57.8 −29.8 −51.8

ρg (g cm−3) Tdech (°C) ΔfHmi (kJ mol−/kJ g−1) V0j (L kg−1) vDk (m s−1) Pl (GPa) Tdetm (°C)

4.8 315 450.1/1545.4 252 5920 33.8 3401

3.1 255 −835.0/−1854.4 270 5600

1.76 194 2113.6/4555.2 722 8365 26.8 3548

1.73 185 829.3/1628.1 881 8806 29.5 3231

Impact sensitivity. bFriction sensitivity. cElectrostatic discharge sensitivity. dNitrogen content. eOxygen balance for CaHbOcNd: 1600(c − a − b/ 2)/MW. fOxygen balance for CaHbOcNd: 1600(c − 2a − b/2)/MW, MW = molecular weight. gDensity measured by gas pycnometer (25 °C). h Temperature of decomposition according to DSC (5 °C min−1). iHeat of formation. jGas volume after detonation. kCalculated detonation velocities. lCalculated detonation pressure. mTemperature of detonation. nRef 10. oRef 6. pRef 22. qRef 14. a

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(3) Deng, M.; Feng, Y.; Zhang, W.; Qi, X.; Zhang, Q. A Green Metal-free Fused-ring Initiating Substance. Nat. Commun. 2019, 10, No. 1339. (4) Zhang, W.; Zhang, J.; Deng, M.; Qi, X.; Nie, F.; Zhang, Q. A Promising High-energy-density Material. Nat. Commun. 2017, 8, No. 181. (5) Liu, Y.; Zhao, G.; Tang, Y.; Zhang, J.; Hu, L.; Imler, G. H.; Parrish, D. A.; Shreeve, J. M. Multipurpose [1,2,4]Triazolo[4,3b][1,2,4,5]tetrazine-based Energetic Materials. J. Mater. Chem. A 2019, 7, 7875−7884. (6) Matyás,̌ R.; Pachman, J. Primary Explosives; Springer: Berlin, 2013; Chapter 5, pp 138−145. (7) Klapötke, T. M. Chemistry of High-Energy Materials, 2nd ed.; Walter de Gruyter: Berlin, 2012; p 19. (8) Ilyushin, M. A.; Tselinsky, I. V.; Shugalei, I. V. Environmentally Friendly Energetic Materials for Initiation Devices. Cent. Eur. J. Energ. Mater. 2012, 9, 293−327 http://www.wydawnictwa.ipo.waw.pl/ cejem/vol-9-4-2012/Ilyushin.pdf . (9) Oyler, K. D. Green Energetic Materials; Brinck, T., Ed.; John Wiley & Sons, 2014; Chapter 5, pp 103−110. (10) Fischer, D.; Klapötke, T. M.; Stierstorfer, J. Potassium 1,1′Dinitramino-5,5′-bistetrazolate: A Primary Explosive with Fast Detonation and High Initiation Power. Angew. Chem., Int. Ed. 2014, 53, 8172−8175. (11) Fischer, D.; Klapötke, T. M.; Stierstorfer, J. 1,5-Di(nitramino)tetrazole: High Sensitivity and Superior Explosive Performance. Angew. Chem., Int. Ed. 2015, 54, 10299−10302. (12) He, C.; Shreeve, J. M. Potassium 4,5-Bis(dinitromethyl)furoxanate: A Green Primary Explosive with a Positive Oxygen Balance. Angew. Chem., Int. Ed. 2016, 55, 772−775. (13) Tang, Y.; He, C.; Mitchell, L. A.; Parrish, D. A.; Shreeve, J. M. Potassium 4, 4′-Bis(dinitromethyl)-3,3′-azofurazanate: A Highly Energetic 3D Metal−Organic Framework as a Promising Primary Explosive. Angew. Chem., Int. Ed. 2016, 55, 5565−5567. (14) Chen, D.; Yang, H.; Yi, Z.; Xiong, H.; Zhang, L.; Zhu, S.; Cheng, G. C8N26H4: An Environmentally Friendly Primary Explosive with High Heat of Formation. Angew. Chem., Int. Ed. 2018, 57, 2081− 2084. (15) Xu, Z.; Cheng, G.; Yang, H.; Ju, X.; Yin, P.; Zhang, J.; Shreeve, J. M. A Facile and Versatile Synthesis of Energetic FurazanFunctionalized 5-Nitroimino-1,2,4-Triazoles. Angew. Chem., Int. Ed. 2017, 56, 5877−5881. (16) Mishina, M. S.; Ivanov, A. Y.; Lobanov, P. S.; Dar’in, D. V. A New Synthesis of 2-Aminoindoles and 6-Aminopyrrolo[3,2-d]-

ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsami.9b08363. Experimental procedures, theoretical calculations, characterization data (infrared, multinuclear NMR spectra, mass spectra, elemental analysis, and DSC measurements) (PDF)

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X-ray crystallographic files for 17·3H2O (CIF)

AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected] (H.Y.). *E-mail: [email protected] (G.C.). ORCID

Hongwei Yang: 0000-0003-4763-2972 Zhenxin Yi: 0000-0001-5691-5507 Wenchao Zhang: 0000-0002-8752-2690 Guangbin Cheng: 0000-0003-0115-2965 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by the Science Challenge Project (TZ2018004) and the National Natural Science Foundation of China (Nos 21676147 and 21875110).

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REFERENCES

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DOI: 10.1021/acsami.9b08363 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX

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DOI: 10.1021/acsami.9b08363 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX