Framework-Interpenetrated Nitrogen-Rich Zn(II) MetalâOrganic

Subscriber access provided by BUFFALO STATE

Article

Framework-Interpenetrated Nitrogen-Rich Zn(II) Metal-Organic Frameworks for Energetic Materials Jian-Di Lin, Fei Chen, Jian-Gang Xu, Fa-Kun Zheng, and Na Wen ACS Appl. Nano Mater., Just Accepted Manuscript • DOI: 10.1021/acsanm.9b01011 • Publication Date (Web): 26 Jul 2019 Downloaded from pubs.acs.org on July 26, 2019

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 26 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Applied Nano Materials

Framework-Interpenetrated Nitrogen-Rich Zn(II) Metal-Organic Frameworks for Energetic Materials Jian-Di Lin *, † , Fei Chen †, Jian-Gang Xu*, ‡, Fa-Kun Zheng*, ‡ , Na Wen § †

Department of Applied Chemistry, College of Life Sciences, Fujian Agriculture and

Forestry University, Fuzhou, Fujian 350002, P. R. China. *Corresponding author, Email: [email protected], [email protected], [email protected]; Tel: +0086-59183750182; Fax: +0086-591-83789352. ‡

State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the

Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, P. R. China. §

College of Materials Science and Engineering, Fuzhou University, Fuzhou, Fujian

350116, P. R. China.

Abstract:

Nitrogen-rich high density metal-organic frameworks (MOFs) can be

used as a new type of energetic materials. The energetic MOFs provide a new method to reconcile contradiction between high energy and reliable safety in energetic materials. Framework interpenetration would be an effective approach to reduce the pore volume and meanwhile to enhance the structural/chemical stabilities of the target energetic MOFs. In this work, mixed ligands of 5-aminotetrazole (HATZ) and tetrazole (HTZ) were chosen to assemble with Zn(II) ion with the purpose to prepare interpenetrated MOF materials with insensitivity. Ultimately, a high-density 3D energetic compound, [Zn2(ATZ)2(TZ)2]n (1) was in situ isolated under the simple hydrothermal conditions. In the crystal structure of 1, there existed two independent 3D diamond networks, which were formed by Zn1(II) ions/TZ− ligands and Zn2(II) ions/ATZ− ligands, respectively. These two independent 3D diamond networks were interpenetrated to each other to construct a 3D condensed high-density framework. The standard molar enthalpy of formation (ΔfHo) of 1 was deduced as 1786.45 kJ/mol (4.09 kJ/g), which to date still occupies the status of the top high ΔfHo value among the reported energetic MOF materials. The conduction of sensitivity measurements demonstrated the insensitivity

ACS Paragon Plus Environment

ACS Applied Nano Materials 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

of 1 to external mechanical stimuli and TGA showed 1 had a good thermal stability which can stabilize up to 332 °C. Whereas the decomposition temperature of pure HATZ and HTZ ligands are 207 °C and 174 °C, respectively, which illuminates that the much more stability of 1 could be attributed to the structural reinforcement induced by the effect of coordination polymerization and framework interpenetration. So compound 1 can serve as a promising energetic material with a good safety level because of its good energetic properties, insensitivity, and high thermal stability.

Keywords:

3D metal-organic framework, framework interpenetration, structural

reinforcement, energetic N-rich compounds; insensitivity.

1. Introduction High-energy materials have already been investigated and applied widely in the area of civilian and military purposes. The development of modern weapons requires that energetic materials must contain high energy and meanwhile have good safety. Therefore, the designed synthesis of high-energy and insensitive materials is a significant research content in the domain of energetic materials.1-6 However, with the improvement of the energy level of energetic materials, their safety is always reduced. How to adjust the material structure and coordinate the contradiction between material energy and stability through effective combination and reasonable arrangement of chemical bonds and structural motifs has become the research focus of research scientist on energetic materials in the world.7-8 Metal-organic frameworks (MOFs) 9-10 have been gained many attentions not only owing to their stable skeletons, controllable structural designs, tunable properties but also because of their promising potential for applications in gases storage or separation, catalysis, sensing, conductivities, second-order non-linear optical materials, drug delivery, ferroelectric materials, and so on.11-27 Since MOFs possess the merits of good heat stability and well mechanical hardness and strength, so it can be foretold that MOFs maybe have potential applications in the energy field by the utilization of highly energetic ligands as coordination ligands. During the past several years, numbers of


Page 2 of 26

Page 3 of 26 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


energetic MOFs with low sensitivities, favorable thermostabilities, remarkable heat of detonation have been reported thanks to their extensive coordination grids and strong structural reinforcements.28-36 Compared with 1D and 2D grids, 3D MOFs normally possesses higher structural reinforcement and thus usually can provide superior energetic performances and larger mechanical strength. The tetrazole or tetrazole derivatives ligands possess abundant coordination modes and thus can provide a good opportunity to build high-dimensional dense complicated nitrogen-rich energetic MOFs.29,

37-39

According to the previous

reports, the ethyl tetrazole-5-carboxylate (ETZC) ligand usually undergoes in situ decarboxylation to produce tetrazole which then coordinates to metal ions under the hydrothermal conditions40-41 while the reaction mechanism of this kind of in situ decarboxylation is still unclear since to the complexity of the hydrothermal reactions. The reactions of Zn(II) and ETZC or HATZ may produce 3D diamond networks. For example, when N, N′-dimethylformamide–azine–dihydrochloride was adopted as structure directing agent, the self-assembly of HATZ with Zn(NO3)2·6H2O in DMF produces [Zn(ATZ)2]·DMF, whose crystal structure is related to diamond (dia) topological net.42 Reaction of Zn(Ac)2·6H2O with HTZ in 2-butanol under solvothermal conditions gives [Zn(TZ)2] as colorless prismatic crystals whose crystal structure also exhibits a diamond like structure.43-44 These two MOFs are both nitrogenrich materials, however, their energetic performances were not carried out. Framework interpenetration can effectively reduce the pore volume, and meanwhile frequently lead to MOFs which possess higher structural and chemical stabilities.45-47 Thus, from the perspective of structure stabilities and energy, framework interpenetration would be an effective strategy to reinforce the structures of energetic materials. As we know, compact 3D MOFs have better energetic performances and thermal stability. So, it could be inferred that if 3D MOFs are interpenetrated to each other, the structural reinforcement would be further strengthened compared with a single 3D MOF, which can be developed into a new type of high-energy insensitive high explosives. The high energy MOFs reported previously are 1D chains, 2D planes and 3D architectures, and to date no interpenetrated energy MOFs was reported.



Considering the energy level of the target compound, high nitrogen content of organic ligands are inclined to be selected to synthesize high energy MOFs. Five-membered Nrich heterocyclic ligands have steady chemical property by reason of their conjugation nature of aromatic rings, for instance, tetrazole, imidazole as well as their corresponding derivatives.48 These types of N-rich organic ligands have high enthalpy of formation that can provide main energy sources of the target MOF materials49. The tetrazole or tetrazole derivatives ligands have very high nitrogen contents, for example, the nitrogen contents of tetrazole (HTZ) and 5-aminotetrazole (HATZ) are 80% and 82.4%, respectively, which are very sensitive.50 Therefore based on these considerations above, in present work, we chose ETZC and HATZ as ligands to react with Zn(II) under hydrothermal conditions hoping to prepare mixed-ligands high-dimensional N-rich interpenetrated MOF materials with high energy and insensitivity (Scheme 1). Nitrogen-rich tetrazole derivatives were used as ligands in this study mainly because of the following two advantageous properties: (i) The tetrazole derivatives have good energy characters; (ii) The flexible coordination modes of tetrazole derivatives provide the possibility to construct complicated high energy MOF materials.29, 37-39 Finally, we fortunately isolated a solvent-free N-rich 3D high-energy MOF, [Zn2(ATZ)2(TZ)2]n (1) through simple hydrothermal techniques. Xray diffraction determination manifests that 1 exihibits a 3D interpenetrated highdensity network. Compound 1 possesses the merits of high thermal stability, high enthalpy of formation (ΔfH°), reliable mechanical sensitivity and marvelous heat of detonation, which are discussed detailedly below.


Page 4 of 26

Page 5 of 26 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Scheme 1 (a) Traditional synthesis method of energetic MOF materials; (b) synthetic strategy of compound 1.

2. Experimental section Caution! The ligands and as-prepared energetic compounds might explode under external stimuli, which should be synthesized and handled carefully. Some appropriate protective precautions such as leather gloves, a face shield and safety glass should be undertaken during treatments. The high-energy MOF materials should be prepared and conducted with little amount.

2.1.

General methods All the chemicals used in present experiment were bought from commercial source

and used directly. A powder diffractometer (Rigaku Miniflex 600) was employed to collect the experimental powder X-ray diffraction (PXRD) pattern (Cu Kα, λ = 1.54056 Å). The data of theoretical PXRD pattern was exported via Mercury 1.4.51 The experiments of DSC and TGA were conducted on METTLER TOLEDO under the atmosphere of N2 (ramp rate: 5 °C/min). The Elementar Vario EL III microanalyzer was used to measure the contents of C, H and N of 1. The fourier transform infrared spectrum (KBr pellet) was recorded on a PerkinElmer Spectrum spectrophotometer. Nitrogen adsorption isotherm was measured on ASAP 2020 System. The sample of 1 was activated at 130 ℃ for 6 h under high vacuum, and the activated sample was denoted as 1-ht.

2.2.

Synthesis of [Zn2(ATZ)2(TZ)2]n (1) The reactants of HATZ (0.5 mmol), ETZC (0.5 mmol) and Zn(NO3)2·6H2O (0.5

mmol) were mixed together and dissolved in distilled H2O (5 mL) in a 20 mL Teflonlined stainless-steel autoclave, which was tightly sealed and heated at 160 °C for 72 h. Then this autoclave was cooled down gradually to indoor temperature with a cooling rate of 5.5 °C per hour. The formed crystals shaping prismatic and pale yellow were gathered and washed adequately in sequence with distilled H2O and CH3CH2OH, and then air-dried (yield: 49 mg, 45% based on Zn(NO3)2·6H2O). Actually, we tried to use HATZ and HTZ to prepare this compound at the outset. However, compound 1 could



not be obtained if HTZ was directly employed as the reactant although several parameters such as temperature, solvent or pH value were adjusted. According to the literature reports, the ethyl tetrazole-5-carboxylate (ETZC) ligand usually undergoes in situ decarboxylation to produce tetrazole (HTZ) which can then directly coordinate to metal ions under the hydrothermal conditions. So, we chose HATZ and ETZC to react with Zn(II) to prepare compound 1. Based on the single-crystal structural analysis, 1 can be formulated as [Zn2(ATZ)2(TZ)2]n. The crystals of 1 were shown in Fig. S1. Elemental analysis (%) of C4H6N18Zn2 (Mr = 437.01), calcd: C 10.98, H 1.37, N 57.66; found: C 11.02, H 1.40, N 57.69. Selected FT-IR (cm−1, KBr): 3448 (m), 3399 (m), 3334 (m), 3198 (m), 3145 (m), 2917 (w), 2807 (w), 2733 (w), 1663 (vs), 1575 (vs), 1467 (vs), 1373 (w), 1340 (s), 1307 (w), 1262 (s), 1164 (vs), 1103 (vs), 1076 (vs), 994 (vs), 899 (s), 764 (w), 743 (m), 681 (vs), 576 (vw), 490 (s) (Fig. S2).

2.3.

X-ray Crystallography X-ray single-crystal diffraction dataset of 1 were obtainedvia a Rigaku Mercury

CCD diffractometer at 293 K using an ω scan technique (graphite-monochromatized Mo-Kα radiation, λ = 0.71073 Å). The CrystalClear programmes was employed to reduce the dataset of 1.52 The multi-scan absorption corrections method was applied to the dataset of 1 and then the structure was solved out via direct methods by SHELXS2014.53-55 The full-matrix least-squares on F2 was adopted to refine all the nonhydrogen atoms of 1. While all the hydrogen atoms of 1 were theoretically positioned and isotopically refined. The detailed information of the crystal parameters and refinements for 1 are listed in Table S1. Selected bond distances and angles for 1 are listed in Table S2. The CCDC Number of 1 is 1893143.

3. Results and discussion 3.1. Structural description of 1 Compound 1 crystallizes in the orthorhombic chiral space group P212121. It should be pointed out that the a-axis and b-axis in the cell parameters of 1 are equal, which normally should be tetragonal system. It is surprising that the structure of 1 could not be solved out with tetragonal system. As far as we know, this phenomenon has not


Page 6 of 26

Page 7 of 26 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


been encountered before. The crystal structure of 1 exhibits a 3D interpenerated condensed skeleton. The theoretical density (ρ) of 1 was 2.143 g/cm3 according to the single-crystal data at 293 K. In the asymmetric unit of 1, there exist two independent Zn(II) ions, two ATZ− anions and two TZ− anions (Fig. 1a). Both two Zn(II) ions are in a little bit distorted tetrahedral environments. The coordination geometry of Zn1(II) ion is completed by N11, N21, N142 and N241 (Fig. 1b) and that of Zn2(II) ion is finished by N31, N41, N343 and N444 (Fig. 1c). The bond lengths of Zn–N in the structure of 1 vary from 1.9734(11) Å to 2.0157(11) Å, which are consistent with those of the previous reports of Zn(II)/heterocyclic nitrogen MOFs.41, 43 The N–Zn–N angles around the Zn1(II) and Zn2(II) ions are ranging from 103.156(23)° to 113.353(24)°, which are adjacent to the angle of the ideal tetrahedron. Both the ATZ− and TZ− ligands adopt the μ2 coordination modes. The TZ− ligands link the Zn1(II) ions to generate a 3D diamond structure and ATZ− ligands connect the Zn2(II) ions to build another 3D diamond architecture. Interestingly, these two independent 3D diamond networks are interpenetrated to each other to construct the final 3D condensed framework (Fig. 2a). The crystal structure of 1 was checked by Platon software and the result show that 1 has no solvent accessible void, which can also be verified by BET experiment (no nitrogen adsorption) (Fig. S3). To the best of our knowledge, the different individual framework interpenetration like in the microstructure of 1 has not been reported before. The formation of framework interpenetration greatly enhances the compactness and improves the structural stability of the target MOF and thus could benefit the energy performance of the target compound. The distances of the neighbouring Zn1(II) ions separated by the TZ− ligands are 6.0889(36) and 6.0554(36) Å, and those between the adjacent Zn2(II) ions linked by the ATZ− ligands are 6.0512(36) and 6.0745(36) Å. From the point of view of topology, the Zn1(II) and Zn2(II) ions can be regarded as four-connected nodes, while the ATZ− and TZ− anions can be abstracted as connectors since each of these ligands is only two-connecting, so the 3D skeleton of 1 could be simplified as a 3D interpenetrated diamond topological net (dia) (Fig. 2b). Within the interpenetrated diamond network, the Zn1–Zn1–Zn1 angles in the Zn1(II)/ATZ− diamond network are revealed to range from 99.537(16)° to 120.721(16)° (Fig. S4) and



those in the Zn2(II)/TZ− diamond network are falling between 103.106(17)° and 116.849(17)° (Fig. S5). These angles deviate seriously from that of an idealized diamond network (109.47°), which suggests that the topological network of compound 1 adopts a highly distorted diamond network. In comparison, self-assembly of Zn(NO3)2·6H2O with HATZ in H2O at 160 °C affords colorless crystals of [Zn2(ATZ)3(ATZ)2/2], whose microstructure is a bilayer honeycomb feature thus shows a 2D unique 4-connected hcb net.56 The reaction of Zn(Ac)2·6H2O, ETZC, NaOH aqueous solution and methanol at 160 °C in situ produces [Zn3(TZ)6(H2O)2], which shows a kagomé dual (kgd) topological layer.41 Considering that 1 crystallizes with a chiral space group, the second-order NLO effect of 1 was also examed qualitatively and no evident second-order NLO signal could be detected.

Fig. 1 (a) The asymmetric unit of 1; (b) the coordination geometry of Zn1(II) and the coordination modes of TZ- in 1; (c) the coordination geometry of Zn2(II) and the coordination modes of ATZ- in 1. Symmetry codes: 1-1/2 + x, 1/2 - y, -z; 2-x, 1/2 + y, 1/2 - z; 31/2 + x, -1/2 - y, -Z; 41 - x, -1/2 + y, 1/2 - z; 51/2 + x, 1/2 - y, -z; 6-x, -1/2 + y, 1/2 - z; 7-1/2 + x, -1/2 - y, -z; 81 - x, 1/2 + y, 1/2 - z.


Page 8 of 26

Page 9 of 26 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Fig. 2 (a) The 3D self-interpenetrated condensed network of 1 viewed along b axis; (b) the 3D topological net for 1 along b axis.

3.2. Stability and thermal behavior of 1 The stability is another important attribute for the practical use of high-energy materials, which was characterized by PXRD, TGA and DSC. Compound 1 can stablilize in air and common solvents such as CH3OH, CH3CH2OH, DMF, and DMSO. To study the chemical stability of 1, one sample of 1 was exposed in air for one month, one sample of 1 was soaked in water for 24 hours and another sample of 1 was heated at 100 °C in water for 30 minutes. For the latter two cases, the samples were collected by filtration and dried before characterizations of PXRD. As shown in Fig. 3, the PXRD patterns (a-e) of 1 were almost similar after treatments of different conditions, which demonstrates that 1 exhibits good steady chemical property in both room temperature water and boiling water and can be stored at room temperature for a long time. The experiment result of the PXRD pattern (b) is in good accordance with that of the simulation result (a), which also indicates the purity of the prepared sample of 1. The PXRD pattern of 1-ht is shown in Fig. 3f, from which we can see that the peaks after activation still correspond well to the simulation peaks. This indicates that the crystallinity of 1-ht still remains unchanged after activation and adsorption.



Fig. 3 PXRD patterns of (a) the simulation result of 1 from single-crystal X-ray data; (b) the freshly prepared sample of 1; (c) 1 exposed in air for one month; (d) 1 soaked in water for 24 hours; and (e) 1 heated at 100 °C in water for thirty minutes; (f) the activated sample 1-ht.

The thermal stability of 1 was evaluated by TGA and DSC techniques in N2 atmosphere (Fig. 4). It can be seen from the TGA plot that no significant weight loss is observed for 1 ranging from room temperature to 332 °C. When continue heating, a sharp peak for weight loss appears and in the meantime most of weight of 1 lost, demonstrating that the framework of 1 suddenly collapses and explodes at 332 °C. The thermostability of 1 can also be ascertained by the DSC technique, and there was no heat flow peak in the DSC curve before 332 °C, which was coincident well with the TGA result. At 357 °C, a sharply exothermic peak appears, demonstating that 1 had exploded around this temperature. Comparatively, the decomposition temperature of pure HTAZ and HTZ ligands are 207 °C57 and 174 °C,58 respectively. That is to say, through the coordination polymerization of Zn(II) ions to aggregate HATZ and HTZ


Page 10 of 26

Page 11 of 26 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


ligands to generate a 3D condensed skeleton, the thermal stability of the resulted MOF 1 has greatly enhanced. The explosion temperature of 1 is far greater than 200 °C, which indicates that 1 can well meet the requirements of practical applications.

Fig. 4 The DSC and TGA plots of 1 measured under N2 atmosphere.

3.3. Heat of combustion Normally, the energetic N–N and C–N bonds of the energetic ligands have high positive heats of formation which could make the N-rich MOF materials energetic. Compound 1 could be used as a promising energetic material on account of its high nitrogen content (57.66%) and high thermal stability. Heat of combustion at constant volume (ΔcU) of 1 was measured via oxygen bomb calorimetry (see Supporting Information) in order to compute the enthalpy of combustion (ΔcH) of 1, and the experimental value of ΔcU is −11.293 kJ/g. The ΔcH of 1 was deduced by the following formula: ΔcH = ΔcU + ΔnRT, in which Δn stands for the change value of the total molar amount of gases in the combustion process, T = 298.15 K and R = 8.314 J·mol−1·K−1. The equation of combustion is provided in Eq. (1) as follows: C4H6N18Zn2 (s) + 6.5O2 (g)  2ZnO (s) + 4CO2 (g) + 3H2O (l) + 9N2 (g)


(1)


Page 12 of 26

As reported, the ΔcH values of RDX, HMX and TNT are −9.60, −9.44 to −9.88 and −16.27 kJ/g, respectively.59 The value ΔcH for 1 deduced by the formula mentioned above is −11.256 kJ/g, which is inferior to that of TNT and exceed those of RDX or HMX. The ΔcH value of 1 is greater than those of most previously reported 3D energetic MOFs, such as [Cu3(MA)2(N3)3] (CuMAA, MA = melamine) (−9.73 kJ/g),28 Cd3(atz)4(N3)2 (CdatzA = Cd3(atz)4(N3)2, Hatz = 3-amino-1, 2, 4-triazole) (−8.561 kJ/g),32 (Et4N)[Cd6Br5(ATZ)8]·H2O (CdATZ, HATZ = 5-aminotetrazolate, Et = ethyl) (−6.672 kJ/g),38 CoBTA (−5.92 kJ/g) (CoBTA = [Co9(BTA)10(HBTA)2(H2O)10]n (H2BTA = N, N′-bis(1H-tetrazole-5-yl)-amine)),60 and comparable to that of the recently reported mixed-ligand 2D energetic MOFs, [Co(N3)2(atrz)]n (−11.939 kJ/g) and [Cd(N3)2(atrz)]n (−10.745 kJ/g) (atrz = 4, 4′-azo-1, 2, 4-triazole). The nitrogen content and calculated density (ρ) of [Co(N3)2(atrz)]n are 63.81% and 2.094 g/cm3, respectively and those of [Cd(N3)2(atrz)]n are 53.99% and 2.282 g/cm3, respectively.61 In 2011, Yang’s group prepared a one dimensional N-rich mixed-ligands Zn(II)-based compound [Zn(N2H4)2(N3)2]n (ZnHA) (N% = 65.6%). The value of ρ and ΔcH of ZnHA were reported to be 2.083 g/cm3 and −5.45 kJ/g, respectively.62 Notwithstanding the nitrogen content of ZnHA is superior to that of 1, the ΔcH value of 1 is far larger than that of ZnHA, the essential reason of which is likely to put down to the one dimension of ZnHA. But the ΔcH value of 1 is smaller than that of [Zn(tzep)(H2O)2]·H2O (H2tzep = N-[2-(1H-tetrazol-5-yl)ethyl]proline), whose ΔcH value is −14.16 kJ/g.63 The standard molar enthalpy of formation (ΔfHo) of 1 was deduced according to law of Hess cycle (Eq. (2)), and calculated to be 1786.45 kJ/mol (4.09 kJ/g) using known molar enthalpies of formation of H2O (l, −285.83 kJ/mol), CO2 (g, −393.51 kJ/mol) and ZnO (s, −350.5 kJ/mol). ΔfHo[1, s] = 2ΔfHo[ZnO, s] + 4ΔfHo[CO2, g] + 3ΔfHo[H2O, l] – ΔcHo[1, s]

(2)

The ΔfHo value for 1 is much greater than those of common high energy compounds such as TNT (−0.2952 kJ/g), HMX (0.3545 kJ/g), RDX (0.4186 kJ/g) 64 (Fig. S6) and Pb(N3)2 (1.5454 kJ/g)65 and comparable to the previously reported energetic MOFs with the currently top high ΔfHo value, for example, CdAatrz (4.08 kJ/g, [Cd(N3)2(atrz)]n),


Page 13 of 26 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


CoAatrz (4.21 kJ/g, [Co(N3)2(atrz)]n),61 CuMAA (4.04 kJ/g, [Cu3(MA)2(N3)3]).28 This extremely high ΔfHo value of 1 may be due to the condensed extensive coordination grids and strong structural reinforcement induced by the framework interpenetration, which make 1 show high energy. Energetic properties for 1, HMX, RDX, TNT and some other high energy MOFs are listed in Table 1. Table 1 Comparison of energetic properties for 1, HMX, RDX, TNT and some other high energy MOFs. Compound

N[a] (%)

Tdec[b] (°C)

ρ[c]

Ω[d]

(g/cm3)

1 (3D)

57.66

332

HMX

37.84

RDX

(%)

ΔfHo[e] (kJ/g)

IS[f] (J)

FS[g] (N)

2.143

–46.70

4.09

>40

>360

280

1.950

–21.62

0.3545

7.4

112

37.84

210

1.806

–21.62

0.4186

7.5

120

TNT

18.50

244

1.654

–74.00

-0.2952

15

353

CoAatrz (2D)

63.81

208

2.094

–57.30

4.21

1.2

5

CdAatrz (2D)

54.39

218

2.282

–48.85

4.08

1.6

12

40.89

372

2.517

–48.83

1.765

>40

>360

CuMAA (3D)

47.55

178

2.096

–43.36

4.04

>40

>360

CoBTA (3D)

59.85

253

1.707

–40.54

0.2942

27

>360

CdatzA (3D)

a

Nitrogen content; b Decomposition temperature; c Density calculated from single crystal X-ray

diffraction data; d Oxygen balance; e Enthalpy of formation; f Impact sensitivity; g Friction sensitivity.

3.4. Detonation property Energetic materials release energy suddenly by detonation. The heat of detonation (ΔHdet) is hard to get via experiments while it is one of the most important parameters to evaluate the energetic performance of high energy compounds. The developed Kamlet-Jacobs analytical approach was selected to reckon the ΔHdet value of 1. Based



Page 14 of 26

on the empirical Kamlet formula, this approach has been employed to evaluate the ΔHdet values of energetic compounds.66 The ΔHdet values obtained from the Kamlet-Jacobs approach are approximate to those calculated from the EXPLO5 software.66-68 In consideration of the deficiency of oxygen, Zn, N, C, H2O and NH3 are hypothesized as the final detonation products of 1. The equation of detonation reaction for 1 is shown as Eq. (3). C4H6N18Zn2  2Zn + 2NH3 + 8N2 + 4C

𝜟𝑯𝒅𝒆𝒕 = ―

(3)

𝚫𝑯𝟎𝒇(𝐝𝐞𝐧𝐨𝐭𝐚𝐭𝐢𝐨𝐧 𝐩𝐫𝐨𝐝𝐮𝐜𝐭𝐬) ‒ 𝚫𝑯𝟎𝒇(𝐞𝐱𝐩𝐥𝐨𝐬𝐢𝐯𝐞) 𝐟𝐨𝐫𝐦𝐮𝐥𝐚 𝐰𝐞𝐢𝐠𝐡𝐭 𝐨𝐟 𝐞𝐱𝐩𝐥𝐨𝐬𝐢𝐯𝐞

(4)

The ΔHdet value is deduced to be 4.298 kJ/g for 1 via equation 4. The noticeably high ΔHdet value of 1 is not only double higher than those of mercury fulminate (MF) (1.735 kJ/g), Lead styphnate (LS) (1.453 kJ/g)69 and lead azide (LA) (1.569 kJ/g),70 but also superior to most of the previously covered energeric MOFs, for instance, CHHP (3.15 kJ/g),31 ZnHHP (2.94 kJ/g),31 Cd3(atz)4(N3)2 (2.009 kJ/g),32 MOFT-CA (2.98 kJ/g),71 and copper(I) 5-nitrotetrazolate (DBX-1) (3.816 kJ/g).72-73 The ΔHdet value of 1 is comparable to those of CoAatrz (4.407 kJ/g) and CdAatrz (4.248 kJ/g).61 These ΔHdet values of 1, commercial primary explosives and previously reported energetic MOFs listed here are shown in Fig. 5 and Table S3. The high ΔHdet value of 1 is probably attributed to the high-energy ligands, many strong coordination bonds, and the condensed microstructure resulted by interpenereation of the two individual diamond networks, in which the high strain energy is saved. Once compound 1 is detonated, the strain energy is released.


Page 15 of 26 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Fig. 5 Bar diagram representation of ΔHdet values for 1, MF, LA, LS and previously reported energetic MOFs.

For energetic materials, the parameters of D and P are all-important factors as D and P are the functions of density (D = detonation velocity, P = detonation pressure).74 To research the detonation characters further, D and P of compound 1 were reckoned via the Kamlet-Jacbos equations66 (5)–(7) which have been applied to previouly reported energetic MOFs (see Supporting Information). D = 1.01 Φ1/2 (1+1.30ρ)

(5)

P = 1.558 Φρ2

(6)

Φ = 31.68 N(MQ)1/2

(7)

The density of 1 at room temperature calculated from X-ray diffraction data is 2.143 g/cm3, which is larger than those of RDX (1.806 g/cm3), TNT (1.654 g/cm3), HMX (1.950 g/cm3), and ε-CL-20 (2.035 g/cm3) and those of most of the energetic MOFs reported previously such as NHP (1.983 g/cm3), CoBTA (1.707 g/cm3), CHP (1.948 g/cm3), CuNaMtta (1.975 g/cm3) and ATRZ-1 (1.68 g/cm3)75 but smaller than that of Cd3(atz)4(N3)2 (2.517 g/cm3) as the cadimun ion contained in this energetic compound



is a much heavier metal ion.32 The values of D and P of 1 are reckoned to be 7.392 km/s and 26.74 GPa, respectively (see Supporting Information). The values of D and P of 1 can be comparable to those of the Coatrz (7.672 km/s and 28.45 GPa) and Cdatrz (7.538 km/s and 28.72 GPa).61 Very recently, professor Guo reported four metal azide-based energetic MOFs, namely [Co(N3)2(btze)]n (D = 7.339 km/s, P = 25.03 Gpa), [Cd(N3)2(btze)]n (D = 7.088 km/s, P = 24.37 Gpa), [Cd2(N3)3Cl(btze)2]n (D = 6.476 km/s, P = 20.49 Gpa) and [Cd2(N3)2Br2(btze)2]n (D = 6.119 km/s, P = 19.25 Gpa) (btze = 1, 2-bis(tetrazol-1-yl)ethane).76 The values of D and P of 1 are approximately equal to those of [Co(N3)2(btze)]n, and much larger than those of [Cd(N3)2(btze)]n, [Cd2(N3)3Cl(btze)2]n and [Cd2(N3)2Br2(btze)2]n. The high D and P values of 1 could be mainly ascribed to its high-density character.

3.5. Sensitivities test The another vital factor to evaluate the practical applications of energetic compounds is sensitivities. The impact sensitivity (IS) of 1 is determined to surpass 40 J, which indicates it is insensitive to impact. The measurement of friction sensitivity (FS) of 1 manifests that compound 1 was unexploded untill up to 360 N, which reveals that it is insensitive to friction (see Supporting Information).77 The values of IS and FS for 1 are much smaller than those of TNT, HMX and RDX. This experimental results show that 1 is insensitive to external stimuli because of its 3D condensed skeleton that may be caused by the framework interpenetration.

4. Conclusions In this work, Zn(II) was selected to react with the elaborate choice of two nitrogenrich ligands, HATZ and ETZC via coordination polymerization strategy under hydrothermal conditions to in situ produce a safe and high-energy solvent-free 3D MOF compound, Zn2(ATZ)2(TZ)2 (1). The ETZC ligand undergoes in situ decarboxylation to produce tetrazole (HTZ) under the hydrothermal conditions. Two individual 3D diamond networks exsit in the microstructure of 1, which are interpenetrated to each other to construct the final 3D condensed high-density framework of 1. Compound 1 shows an extremely high detonation temperature (much bigger than 200 °C),


Page 16 of 26

Page 17 of 26 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


mechanical insensitivities and good energetic properties. Notably, 1 almost occupies the status of top high ΔfHo value (1786.45 kJ/mol or 4.09 kJ/g) among all the previously covered energetic MOFs. The ΔHdet value of 1 (4.298 kJ/g) is superior to most of the energeric MOFs covered previously. The good energetic properties of 1 could be attributed to its condensed interior structure and the strong structural reinforcement resulted by the framework interpenetration and a great many of strong coordination bonds. The successfully isolated of 1 demonstrates that framework interpenetration could be adopted as another effective strategy to prepare high density N-rich highenergy MOF compounds with predictable performances and excellent energetic properties.

Supporting Information Energy measurement details, energy calculation processes, the picture of the crystals of 1, the fourier transform infrared spectrum for 1, additional tables and figures, and the structures of TNT, RDX and HMX.

Conflicts of interest The anthors declare no conflicts of interest.

Acknowledgment This work has been sponsored by the funding of China Postdoctoral Science Foundation (2017M612106 and 2018M642581), National Natural Science Foundation

of China (31770678), the Open Fund of State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences (20160025).

References 1.

Zhang, T.-L.; Wu, B.-D.; Yang, L., Recent Research Progresses in Energetic

Coordination Compounds. Chinese J. Energ. Mater. 2013, 21 (2), 137-151. 2.

Dong, H.-S., The Development and Countermeasure of High Energy Density

Materials. Chinese J. Energ. Mater. 2004, 12(Suppl.), 1-12. 3.

Wang, Q.; Han, J.; Zhang, Y.; Yan, Z.; Velasco, E.; Yang, L.; Wang, B.; Zang, S.-



Q., Fabrication of Copper Azide Film through Metal-Organic Framework for MicroInitiator Applications. ACS Appl. Mater. Interfaces 2019, 11 (8), 8081-8088. 4.

Ma, X.; Cai, C.; Sun, W.; Song, W.; Ma, Y.; Liu, X.; Xie, G.; Chen, S.; Gao, S.,

Enhancing Energetic Performance of Multinuclear Ag(I)-Cluster MOF-Based HighEnergy-Density Materials by Thermal Dehydration. ACS Appl. Mater. Interfaces 2019, 11 (9), 9233-9238. 5.

Sun, Q.; Li, X.; Lin, Q.; Lu, M., Dancing with 5-Substituted Monotetrazoles,

Oxygen-rich Ions, and Silver: towards Primary Explosives with Positive Oxygen Balance and Excellent Energetic Performance. J. Mater. Chem. A 2019, 7 (9), 46114618. 6.

Yang, J.; Yin, X.; Wu, L.; Wu, J.; Zhang, J.; Gozin, M., Alkaline and Earth

Alkaline Energetic Materials Based on a Versatile and Multifunctional 1Aminotetrazol-5-one Ligand. Inorg. Chem. 2018, 57 (24), 15105-15111. 7.

Dippold, A. A.; Klapötke, T. M., A Study of Dinitro-bis-1, 2, 4-triazole-1, 1′-diol

and Derivatives: Design of High-Performance Insensitive Energetic Materials by the Introduction of N-Oxides. J. Am. Chem. Soc. 2013, 135 (26), 9931-9938. 8.

Joo, Y.-H.; Shreeve, J. M., Nitroimino-tetrazolates and Oxy-nitroimino-

tetrazolates. J. Am. Chem. Soc. 2010, 132 (42), 15081-15090. 9.

Furukawa, S.; Reboul, J.; Diring, S.; Sumida, K.; Kitagawa, S., Structuring of

Metal-Organic Frameworks at the Mesoscopic/Macroscopic Scale. Chem. Soc. Rev. 2014, 43 (16), 5700-5734. 10. Ferey, G., Hybrid Porous Solids: Past, Present, Future. Chem. Soc. Rev. 2008, 37 (1), 191-214. 11. Zhao, J.; Dong, W.-W.; Wu, Y.-P.; Wang, Y.-N.; Wang, C.; Li, D.-S.; Zhang, Q.C., Two (3, 6)-Connected Porous Metal-Organic Frameworks Based on Linear Trinuclear [Co3(COO)6] and Paddlewheel Dinuclear [Cu2(COO)4] SBUs: Gas Adsorption, Photocatalytic Behaviour, and Magnetic Properties. J. Mater. Chem. A 2015, 3 (13), 6962-6969. 12. Lin, J.-D.; Long, X.-F.; Lin, P.; Du, S.-W., A Series of Cation-Templated, Polycarboxylate-Based Cd(II) or Cd(II)/Li(I) Frameworks with Second-Order


Page 18 of 26

Page 19 of 26 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Nonlinear Optical and Ferroelectric Properties. Cryst. Growth Des. 2010, 10 (1), 146157. 13. Zhao, Y.; Song, Z.; Li, X.; Sun, Q.; Cheng, N.; Lawes, S.; Sun, X., Metal Organic Frameworks for Energy Storage and Conversion. Energ. Storage Mater. 2016, 2 (Supplement C), 35-62. 14. Lin, J.-D.; Rong, C.; Lv, R.-X.; Wang, Z.-J.; Long, X.-F.; Guo, G.-C.; Pan, C.-Y., A 3D Metal-Organic Framework with a pcu Net Constructed from Lead(II) and Thiophene-2, 5-dicarboxylic Acid: Synthesis, Structure and Ferroelectric Property. J. Solid State Chem. 2018, 257, 34-39. 15. Wang, L.; Han, Y.; Feng, X.; Zhou, J.; Qi, P.; Wang, B., Metal-Organic Frameworks for Energy Storage: Batteries and Supercapacitors. Coord. Chem. Rev. 2016, 307 (Part 2), 361-381. 16. Chen, B.; Yang, Y.; Zapata, F.; Lin, G.; Qian, G.; Lobkovsky, E. B., Luminescent Open Metal Sites within a Metal-Organic Framework for Sensing Small Molecules. Adv. Mater. 2007, 19 (13), 1693-1696. 17. Duan, J.; Zhang, Q.; Wang, S.; Zhou, B.; Sun, J.; Jin, W., Controlled Flexibility of Porous Coordination Polymers by Shifting the Position of the –CH3 Group around Coordination Sites and their Highly Efficient Gas Separation. Inorg. Chem. Front. 2018, 5 (8), 1780-1786. 18. Lin, J.-D.; Clérac, R.; Rouzières, M.; Venkatesan, M.; Chimamkpam, T. O.; Schmitt, W., Exploring the Coordination Chemistry of Bifunctional Organoarsonate Ligands: Syntheses and Characterisation of Coordination Polymers that Contain 4-(1, 2, 4-triazol-4-yl)phenylarsonic Acid. CrystEngComm 2014, 16 (34), 7894-7905. 19. Gheorghe, A.; Tepaske, M. A.; Tanase, S., Homochiral Metal-Organic Frameworks as Heterogeneous Catalysts. Inorg. Chem. Front. 2018, 5 (7), 1512-1523. 20. Lin, J.-D.; I. Onet, C.; Schmitt, W., Photoluminescent Lead(II) Coordination Polymers Stabilised by Bifunctional Organoarsonate Ligands. Sci. Technol. Adv. Mater. 2015, 16 (2), 024803. 21. Lin, Z.-J.; Zheng, H.-Q.; Zheng, H.-Y.; Lin, L.-P.; Xin, Q.; Cao, R., Efficient Capture and Effective Sensing of Cr2O72– from Water Using a Zirconium Metal-



Organic Framework. Inorg. Chem. 2017, 56 (22), 14178-14188. 22. Diamantis, S. A.; Margariti, A.; Pournara, A. D.; Papaefstathiou, G. S.; Manos, M. J.; Lazarides, T., Luminescent Metal-Organic Frameworks as Chemical Sensors: Common Pitfalls and Proposed Best Practices. Inorg. Chem. Front. 2018, 5 (7), 14931511. 23. Zeng, X.-S.; Xu, H.-L.; Xu, Y.-C.; Li, X.-Q.; Nie, Z.-Y.; Gao, S.-Z.; Xiao, D.-R., A Series of Porous Interpenetrating Metal-Organic Frameworks Based on Fluorescent Ligands for Nitroaromatic Explosive Detection. Inorg. Chem. Front. 2018, 5 (7), 16221632. 24. Zheng, H.-Q.; Liu, C.-Y.; Zeng, X.-Y.; Chen, J.; Lü, J.; Lin, R.-G.; Cao, R.; Lin, Z.-J.; Su, J.-W., MOF-808: A Metal-Organic Framework with Intrinsic PeroxidaseLike Catalytic Activity at Neutral pH for Colorimetric Biosensing. Inorg. Chem. 2018, 57 (15), 9096-9104. 25. Cheng, Y.-J.; Wang, R.; Wang, S.; Xi, X.-J.; Ma, L.-F.; Zang, S.-Q., Encapsulating [Mo3S13]2− Clusters in Cationic Covalent Organic Frameworks: Enhancing Stability and Recyclability by Converting a Homogeneous Photocatalyst to a Heterogeneous Photocatalyst. Chem. Commun. 2018, 54 (96), 13563-13566. 26. Zhao, Y.; Wang, L.; Fan, N.-N.; Han, M.-L.; Yang, G.-P.; Ma, L.-F., Porous Zn(II)Based Metal-Organic Frameworks Decorated with Carboxylate Groups Exhibiting High Gas Adsorption and Separation of Organic Dyes. Cryst. Growth Des. 2018, 18 (11), 7114-7121. 27. Zhao, Y.; Yang, X.-G.; Lu, X.-M.; Yang, C.-D.; Fan, N.-N.; Yang, Z.-T.; Wang, L.-Y.; Ma, L.-F., {Zn6} Cluster Based Metal-Organic Framework with Enhanced Room-Temperature Phosphorescence and Optoelectronic Performances. Inorg. Chem. 2019, 58 (9), 6215-6221. 28. Zhang , H.; Zhang , M.; Lin , P.; Malgras, V.; Tang , J.; Alshehri, S. M.; Yamauchi , Y.; Du, S.; Zhang, J., A Highly Energetic N-Rich Metal-Organic Framework as a New High-Energy-Density Material. Chem. Eur. J. 2016, 22 (3), 1141-1145. 29. Qin, J.-S.; Zhang, J.-C.; Zhang, M.; Du, D.-Y.; Li, J.; Su, Z.-M.; Wang, Y.-Y.; Pang, S.-P.; Li, S.-H.; Lan, Y.-Q., A Highly Energetic N-Rich Zeolite-Like Metal-


Page 20 of 26

Page 21 of 26 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Organic Framework with Excellent Air Stability and Insensitivity. Adv. Sci. 2015, 2 (12), 1500150. 30. Chen, D.; Jing, D.; Zhang, Q.; Xue, X.; Gou, S.; Li, H.; Nie, F., Study of Six Green Insensitive High Energetic Coordination Polymers Based on Alkali/Alkali‐Earth Metals and 4, 5‐Bis(tetrazol‐5‐yl)‐2H‐1, 2, 3‐triazole. Chem. Asian. J. 2017, 12 (24), 3141-3149. 31. Bushuyev, O. S.; Peterson, G. R.; Brown, P.; Maiti, A.; Gee, R. H.; Weeks, B. L.; Hope-Weeks, L. J., Metal-Organic Frameworks (MOFs) as Safer, Structurally Reinforced Energetics. Chem. Eur. J. 2013, 19 (5), 1706-1711. 32. Lin, J.-D.; Li, Y.-H.; Xu, J.-G.; Zheng, F.-K.; Guo, G.-C.; Lv, R.-X.; He, W.-C.; Huang, Z.-N.; Liu, J.-F., Stabilizing Volatile Azido in a 3D Nitrogen-Rich Energetic Metal–Organic Framework with Excellent Energetic Performance. J. Solid State Chem. 2018, 265, 42-49. 33. Zhang, Q.; Shreeve, J. M., Metal-Organic Frameworks as High Explosives: A New Concept for Energetic Materials. Angew. Chem. Int. Ed. 2014, 53 (10), 2540-2542. 34. Liu, X.; Gao, W.; Sun, P.; Su, Z.; Chen, S.; Wei, Q.; Xie, G.; Gao, S., Environmentally Friendly High-energy MOFs: Crystal Structures, Thermostability, Insensitivity and Remarkable Detonation Performances. Green Chem. 2015, 17 (2), 831-836. 35. Liu, X.; Qu, X.; Zhang, S.; Ke, H.; Yang, Q.; Shi, Q.; Wei, Q.; Xie, G.; Chen, S., High-Performance Energetic Characteristics and Magnetic Properties of a ThreeDimensional Cobalt(II) Metal-Organic Framework Assembled with Azido and Triazole. Inorg. Chem. 2015, 54 (23), 11520-11525. 36. Zhang, S.; Yang, Q.; Liu, X.; Qu, X.; Wei, Q.; Xie, G.; Chen, S.; Gao, S., HighEnergy Metal-Organic Frameworks (HE-MOFs): Synthesis, Structure and Energetic Performance. Coord. Chem. Rev. 2016, 307, 292-312. 37. Feng, Y.; Liu, X.; Duan, L.; Yang, Q.; Wei, Q.; Xie, G.; Chen, S.; Yang, X.; Gao, S., In situ Synthesized 3D Heterometallic Metal-Organic Framework (MOF) as a HighEnergy-Density Material Shows High Heat of Detonation, Good Thermostability and Insensitivity. Dalton Trans. 2015, 44 (5), 2333-2339.



38. Lin, J.-D.; Wang, S.-H.; Cai, L.-Z.; Zheng, F.-K.; Guo, G.-C.; Huang, J.-S., Tetraalkylammonium Cations as Templates in the Construction of Two Cadmium(ii) Metal-Organic Frameworks. CrystEngComm 2013, 15 (5), 903-910. 39. Yang, Q.; Yang, G.; Zhang, W.; Zhang, S.; Yang, Z.; Xie, G.; Wei, Q.; Chen, S.; Gao, S., Superior Thermostability, Good Detonation Properties, Insensitivity, and the Effect on the Thermal Decomposition of Ammonium Perchlorate for a New SolventFree 3D Energetic PbII-MOF. Chem. Eur. J. 2017, 23 (38), 9149-9155. 40. Zhong, D.-C.; Lin, J.-B.; Lu, W.-G.; Jiang, L.; Lu, T.-B., Strong Hydrogen Binding within a 3D Microporous Metal-Organic Framework. Inorg. Chem. 2009, 48 (18), 8656-8658. 41. Zhong, D.-C.; Lu, W.-G.; Jiang, L.; Feng, X.-L.; Lu, T.-B., Three Coordination Polymers Based on 1H-Tetrazole (HTz) Generated via in Situ Decarboxylation: Synthesis, Structures, and Selective Gas Adsorption Properties. Cryst. Growth Des. 2010, 10 (2), 739-746. 42. Panda, T.; Pachfule, P.; Chen, Y.; Jiang, J.; Banerjee, R., Amino Functionalized Zeolitic Tetrazolate Framework (ZTF) with High Capacity for Storage of Carbon Dioxide. Chem. Commun. 2011, 47 (7), 2011-2013. 43. Wang, X.-S.; Tang, Y.-Z.; Huang, X.-F.; Qu, Z.-R.; Che, C.-M.; Chan, P. W. H.; Xiong, R.-G., Syntheses, Crystal Structures, and Luminescent Properties of Three Novel Zinc Coordination Polymers with Tetrazolyl Ligands. Inorg. Chem. 2005, 44 (15), 5278-5285. 44. Zulipiya, A.; Gao, S.-Y.; Mannsuer, N.; Wang, Y.-B.; Dilinur, M., Structural Characterization and Fluorescence of Zinc Complex with 5-Aminotetrazole Ligands. Chem. Word 2014, 6, 330-332. 45. Marshall, R. J.; Lennon, C. T.; Tao, A.; Senn, H. M.; Wilson, C.; Fairen-Jimenez, D.; Forgan, R. S., Controlling Interpenetration through Linker Conformation in the Modulated Synthesis of Sc Metal-Organic Frameworks. J. Mater. Chem. A 2018, 6 (3), 1181-1187. 46. Jiang, H.-L.; Makal, T. A.; Zhou, H.-C., Interpenetration Control in Metal-Organic Frameworks for Functional Applications. Coord. Chem. Rev. 2013, 257 (15), 2232-


Page 22 of 26

Page 23 of 26 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


2249. 47. Gong, Y.-N.; Zhong, D.-C.; Lu, T.-B., Interpenetrating Metal-Organic Frameworks. CrystEngComm 2016, 18 (15), 2596-2606. 48. Ye, Y.; Zhang, L.; Peng, Q.; Wang, G.-E.; Shen, Y.; Li, Z.; Wang, L.; Ma, X.; Chen, Q.-H.; Zhang, Z.; Xiang, S., High Anhydrous Proton Conductivity of ImidazoleLoaded Mesoporous Polyimides over a Wide Range from Subzero to Moderate Temperature. J. Am. Chem. Soc. 2015, 137 (2), 913-918. 49. Talawar, M. B.; Sivabalan, R.; Mukundan, T.; Muthurajan, H.; Sikder, A. K.; Gandhe, B. R.; Rao, A. S., Environmentally Compatible Next Generation Green Energetic Materials (GEMs). J. Hazard. Mater. 2009, 161 (2), 589-607. 50. Gao, H.; Shreeve, J. M., Azole-Based Energetic Salts. Chem. Rev. 2011, 111 (11), 7377-7436. 51. Macrae, C. F.; Bruno, I. J.; Chisholm, J. A.; Edgington, P. R.; McCabe, P.; Pidcock, E.; Rodriguez-Monge, L.; Taylor, R.; van de Streek, J.; Wood, P. A., Mercury CSD 2.0 - New Features for the Visualization and Investigation of Crystal Structures. J. Appl. Crystallogr. 2008, 41 (2), 466-470. 52. CrystalClear, Version 1.35 ed., Rigaku Corp., Tokyo, Japan. 2001. 53. Sheldrick, G. M., SHELXT-2014, Program for Crystal Structure Solution, University of Göttingen. 2014. 54. Sheldrick, G., A Short History of SHELX. Acta Crystallogr. Sect. A 2008, 64 (1), 112-122. 55. Sheldrick, G. M., Crystal Structure Refinement with SHELXL. Acta Crystallogr. Sect. C 2015, 71 (1), 3-8. 56. Wang, X. W.; Chen, J.-Z.; Liu, J.-H., Photoluminescent Zn(II) Metal-Organic Frameworks Built from Tetrazole Ligand: 2D Four-Connected Regular Honeycomb (4363)-net. Cryst. Growth Des. 2007, 7 (7), 1227-1229. 57. Levchik, S. V.; Ivashkevich, O. A.; Balabanovich, A. I.; Lesnikovich, A. I.; Gaponik, P. N.; Costa, L., Thermal Decomposition of Aminotetrazoles: Part 1. 5Aminotetrazole. Thermochim. Acta 1992, 207, 115-130. 58. Lesnikovich, A. I.; Ivashkevich, O. A.; Lyutsko, V. A.; Printsev, G. V.; Kovalenko,



K. K.; Gaponik, P. N.; Levchik, S. V., Thermal Decomposition of Tetrazole: Part I. Programmed Heating. Thermochim. Acta 1989, 145, 195-202. 59. Ou, Y.-X., Explosives. Beijing Institute of Technology Press, China 2006, 143. 60. Zhang, S.; Liu, X.; Yang, Q.; Su, Z.; Gao, W.; Wei, Q.; Xie, G.; Chen, S.; Gao, S., A New Strategy for Storage and Transportation of Sensitive High-Energy Materials: Guest-Dependent Energy and Sensitivity of 3D Metal-Organic-Framework-Based Energetic Compounds. Chem. Eur. J. 2014, 20 (26), 7906-7910. 61. Xu, J.-G.; Sun, C.; Zhang, M.-J.; Liu, B.-W.; Li, X.-Z.; Lu, J.; Wang, S.-H.; Zheng, F.-K.; Guo, G.-C., Coordination Polymerization of Metal Azides and Powerful Nitrogen-Rich Ligand toward Primary Explosives with Excellent Energetic Performances. Chem. Mater. 2017, 29 (22), 9725-9733. 62. Wu, B.-D.; Yang, L.; Wang, S.-W.; Zhang, T.-L.; Zhang, J.-G.; Zhou, Z.-N.; Yu, K.-B., Preparation, Crystal Structure, Thermal Decomposition, and Explosive Properties of a Novel Energetic Compound [Zn(N2H4)2(N3)2]n: A New High-Nitrogen Material (N = 65.60 %). Z. Anorg. Allg. Chem. 2011, 637 (3-4), 450-455. 63. Wang, S.-H.; Zheng, F.-K.; Zhang, M.-J.; Liu, Z.-F.; Chen, J.; Xiao, Y.; Wu, A. Q.; Guo, G.-C.; Huang, J.-S., Homochiral Zinc(II) Coordination Compounds Based on In-Situ-Generated Chiral Amino Acid-Tetrazole Ligands: Circular Dichroism, Excitation Light-Induced Tunable Photoluminescence, and Energetic Performance. Inorg. Chem. 2013, 52 (17), 10096-10104. 64. Xu, J.-G.; Wang, S.-H.; Zhang, M.-J.; Sun, C.; Xiao, Y.; Li, R.; Zheng, F.-K.; Guo, G.-C.; Huang, J.-S., Nitrogen-Rich Tetranuclear Metal Complex as a New Structural Motif for Energetic Materials. ACS Omega 2017, 2 (1), 346-352. 65. 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 (18), 5565-5567. 66. Wang, Y.; Zhang, J.; Su, H.; Li, S.; Zhang, S.; Pang, S., A Simple Method for the Prediction of the Detonation Performances of Metal-Containing Explosives. J. Phys. Chem. A 2014, 118 (25), 4575-4581.


Page 24 of 26

Page 25 of 26 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


67. Zhang, J.; Du, Y.; Dong, K.; Su, H.; Zhang, S.; Li, S.; Pang, S., Taming Dinitramide Anions within an Energetic Metal-Organic Framework: A New Strategy for Synthesis and Tunable Properties of High Energy Materials. Chem. Mater. 2016, 28 (5), 1472-1480. 68. Li, C.; Zhang, M.; Chen, Q.; Li, Y.; Gao, H.; Fu, W.; Zhou, Z., Three-Dimensional Metal-Organic Framework as Super Heat-Resistant Explosive: Potassium 4-(5-Amino3-Nitro-1H-1, 2, 4-Triazol-1-Yl)-3, 5-Dinitropyrazole. Chem. Eur. J. 2017, 23 (7), 1490-1493. 69. Agrawal, J. P., High Energy Materials Propellants. Explosives and Pyrotechnics. Wiley-VCH: Weinheim, Germany 2010. 70. 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 (31), 8172-8175. 71. Wang, Q.; Feng, X.; Wang, S.; Song, N.; Chen, Y.; Tong, W.; Han, Y.; Yang, L.; Wang, B., Metal‐Organic Framework Templated Synthesis of Copper Azide as the Primary Explosive with Low Electrostatic Sensitivity and Excellent Initiation Ability. Adv. Mater. 2016, 28 (28), 5837-5843. 72. Fronabarger, J. W.; Williams, M. D.; Sanborn, W. B.; Bragg, J. G.; Parrish, D. A.; Bichay, M., DBX-1 – A Lead Free Replacement for Lead Azide. Propell. Explos. Pyrot. 2011, 36 (6), 541-550. 73. Klapötke, T. M.; Piercey, D. G.; Mehta, N.; Oyler, K. D.; Jorgensen, M.; Lenahan, S.; Salan, J. S.; Fronabarger, J. W.; Williams, M. D., Preparation of High Purity Sodium 5-Nitrotetrazolate (NaNT): An Essential Precursor to the Environmentally Acceptable Primary Explosive, DBX-1. Z. Anorg. Allg. Chem. 2013, 639 (5), 681-688. 74. Seth, S.; McDonald, K. A.; Matzger, A. J., Metal Effects on the Sensitivity of Isostructural Metal-Organic Frameworks Based on 5-Amino-3-nitro-1H-1, 2, 4-triazole. Inorg. Chem. 2017, 56 (17), 10151-10154. 75. McDonald, K. A.; Seth, S.; Matzger, A. J., Coordination Polymers with High Energy Density: An Emerging Class of Explosives. Cryst. Growth Des. 2015, 15 (12), 5963-5972.



76. Xu, J.-G.; Li, X.-Z.; Wu, H.-F.; Zheng, F.-K.; Chen, J.; Guo, G.-C., Substitution of Nitrogen-Rich Linkers with Insensitive Linkers in Azide-Based Energetic Coordination Polymers toward Safe Energetic Materials. Cryst. Growth Des. 2019, 19 (7), 3934-3944. 77. Impact: insensitive > 40 J, less sensitive ≥ 35 J, sensitive ≥ 4 J, very sensitive ≤ 3 J; Friction: insensitive > 360 N, less sensitive = 360 N, 80 N < sensitive < 360 N, very sensitive ≤ 80 N, extremely sensitive ≤ 10 N.

TOC Graphic


Page 26 of 26

Framework-Interpenetrated Nitrogen-Rich Zn(II) MetalâOrganic

Recommend Documents

Framework-Interpenetrated Nitrogen-Rich Zn(II) MetalâOrganic