Article pubs.acs.org/IC
High-Performance Energetic Characteristics and Magnetic Properties of a Three-Dimensional Cobalt(II) Metal−Organic Framework Assembled with Azido and Triazole Xiangyu Liu,†,‡,§ Xiaoni Qu,†,§ Sheng Zhang,† Hongshan Ke,† Qi Yang,† Quan Shi,⊥ Qing Wei,† Gang Xie,† and Sanping Chen*,† †
Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi’an 710075, China ‡ School of Chemistry and Chemical Engineering, Ningxia University, Yinchuan 750021, China ⊥ Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023, China S Supporting Information *
ABSTRACT: A three-dimensional metal−organic framework based, high-energydensity compound, [Co5(3-atrz)7(N3)3] (3-atrz = 3-amine-1H-1,2,4-triazole), features superior detonation properties, insensitivity, and thermostability. Magnetic studies show that the compound characterizes the coexistence of remarkable coercivity, metamagnetism, long-range ordering, and relaxation dynamics. The heat-capacity measurement confirms the typical long-range antiferromagnetic ordering below 16 K. This difunctional system exemplifies an effective attempt at developing advanced magnetoenergetic materials.
1. INTRODUCTION Inspired by the intriguing variety of architectures of metal− organic frameworks (MOFs)1−4 and potentially wide applications in the fields of coordination and materials chemistry,5−8 MOFs with high nitrogen content have attracted increasing interest in the area of high-energy-density materials (HEDMs).9 On the basis of the coordination chemistry, the strategy of the rational design and synthesis of energetic MOFs would achieve the gathering of energetic groups (e.g., −NO2, −NH2, N3−) in a relatively small volume, resulting in high density and outstanding detonation properties.10 In addition, the well-ordered distribution of atoms in energetic MOFs plays a significant role in the inherent structural stability and high mechanical strength, which leads to relatively superior thermostability and insensitivity.11 Considering the above, energetic MOFs with high density, high heat of detonation, and rigid structure impel researchers to explore their remarkable potential applications as new generational HEDMs.12 During the past 2 years, one-dimensional (1D) and onedimensional (2D) energetic MOFs with good detonation performance and heat of detonation have been reported by Hope-Weeks and co-workers.13a,b It is followed that, in 2013, Pang14 reported two three-dimensional (3D) MOFs constructed by a nitrogen-rich ligand, 4,4′-azo-1,2,4-triazole (ATRZ), displaying excellent thermal stability and physical and denotation properties. In 2014, Zhang and Shreeve15 © XXXX American Chemical Society
highlighted the potential applications and development prospects of energetic MOFs in the field of HEDMs. In addition, we prepared a 3D porous MOF with a nitrogen-rich ligand, exemplifying that guest molecules have a great influence on the energy and sensitivity.16 The above exemplifies that the sensitivity of energetic MOFs does not increase sharply as the nitrogen content is raised, especially for 3D MOFs, which is derived from the intrinsically unique structure of 3D MOFs.17 Actually, in early 2009, we successfully synthesized a 3D CoIIMOF with high nitrogen content (N = 51.68%).18 Rather than a structural investigation, it would be more worthwhile to further expand the potentially significant energetic properties, including the detonation performance, sensitivity, and thermostability, especially for the energetic MOFs incorporating the simple and stable energy units triazole and azido. Remarkably, as noticed, there are five CoII ions with large magnetic anisotropy in the 3D MOF framework acting in important roles in the construction of molecular-based magnetic materials,19−24 which are both bridged by 3-amine1H-1,2,4-triazole (3-Hatrz) and azido linkers verified to be efficient magnetic mediators.25−29 For instance, Gao et al.30 referenced two molecular magnets consisting of CoII ions and azido groups and illustrated the correlation between the Received: September 24, 2015
A
DOI: 10.1021/acs.inorgchem.5b02196 Inorg. Chem. XXXX, XXX, XXX−XXX
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Inorganic Chemistry
Figure 1. (a) Linear trinuclear unit. (b) Bimetal unit. (c) Manner of cross-stacking. The −NH2 and H atoms are omitted.
Table 1. Detonation Properties for the Compound and Some Energetic Materials compound 13c
3-atrz NaN313d 1 TNT13a RDX13a ATRZ-114 ATRZ-214 CHHP13b ZnHHP13b
ρa (g cm−3)
Nb (%)
Tdecc (°C)
Qd (kcal g−1)
De (km s−1)
Pf (GPa)
1.50 1.846 1.833 (1.826j) 1.654 1.806 1.68 2.16 2.000 2.117
66.65 64.64 51.68 18.50 37.80 53.35 43.76 23.58 23.61
0.227 0.384 3.629 0.897 1.386 3.618 1.381 0.750 0.700
5.91
13.79
410 285 244 210 243 257 231 293
8.749 7.178 8.600 9.160 7.773 6.205 7.016
34.32 20.50 33.92 35.68 29.70 17.96 23.58
ISg (J)
FSh (N)
>5013d >40 15 7.5 22.5 30 0.8
013d >360 353 120 >360 >360
ESDi (J)
>24.75 0.1−0.2 24.75 >24.75
a
From X-ray diffraction. bNitrogen content. cDecomposition temperature. dHeat of detonation. eDetonation velocity. fDetonation pressure. gImpact sensitivity. hFriction sensitivity. iElectrostatic discharge sensitivity. ATRZ-1 = copper 4,4′-azo-1,2,4-triazole nitrate; ATRZ-2 = silver 4,4′-azo-1,2,4triazole nitrate; CHHP = cobalt hydrazine hydrazinecarboxylate perchlorate; ZnHHP = zinc hydrazine hydrazinecarboxylate perchlorate. jDensity measured by a gas pycnometer (25 °C).
structure and magnetism. In 2013, Murugesu et al.31 obtained two CoII-MOFs with an asymmetric triazole ligand, elucidating the exotic magnetic behavior. As for the 3D CoII-MOF obtained in our previous study,18 the systematical investigation on the magnetic properties would contribute to excavation of the potential magnetic value of the title compound. In addition, heat-capacity calorimetry is considered to be a unique method to investigate the chemical and physical properties of the materials at low temperatures32−34 because the heat capacity is a bulk measurement.35 Especially, it is extremely sensitive to crystallographic and magnetic phase transitions, leading to insight regarding long- and short-range ordering and the nature of the ordering. In view of the considerations above, we primarily focus our attention on the study of the energetic characteristics of the 3D MOF-based high-energy compound [Co5(3-atrz)7(N3)3] (1). The results demonstrate that compound 1 displays remarkable physicochemical properties, indicating that 1 could be employed as potential explosives. As we expected, lowtemperature magnetic measurements illustrate that 1 performs fascinating magnetic behaviors, such as dramatic coercivity, weak slow relaxation, and so on. The heat capacity (Cp) of 1 has been measured to correspond to the magnetic results. The present candidate would be anticipated as the preeminently multifunctional materials applied in magnetoenergetic fields.
reaction according to our previous work.18 The obtained product was determined by elemental analysis, IR, and powder X-ray diffraction (PXRD; see the Supporting Information). Although the single-crystal X-ray structure of the compound has been described previously,18 the terse structure expression is indispensable in order to correlate the structure and property. 1 crystallizes in the orthorhombic space group Pccn, in which the asymmetric unit is crystallographically independent with two and a half CoII ions (Co1, Co2, and Co3), three and a half 3-atrz ligands, and one and a half azido groups. The distorted octahedral Co1 and Co2 ions are bridged by adjacent μ1,2,4-3atrz and azido groups, generating a 1D CoII ion chain (Figure 1a). Two adjacent Co3 ions with tetrahedral geometry are connected by two N atoms from one μ1,4-3-atrz ligand, forming the bimetal unit [Co-(μ1,4-3-atrz)-Co] (Figure 1b). The 1D chains paralleling each other along two directions (layers A and B in Figure 1c) are linked by the bimetal unit to yield a 3D architectural framework, as shown in Figure 1c. 2.2. Thermal Decomposition, Detonation Properties, and Nonisothermal Kinetic Analysis. 2.2.1. Thermal Decomposition of 1. The thermostability of 1 has been determined by thermogravimetric analysis with a heating rate of 5 °C min−1.18 A sudden collapse of the main framework occurs at a decomposition temperature of 285 °C. The good stability and high energy were also clarified by the differential scanning calorimetry curve, showing that one intense exothermic process appears at 285 °C and ends at 395 °C with a peak temperature of 344 °C. The observed drastic decomposition process drives us to consider the detonation performance of the compound.
2. RESULTS AND DISCUSSION 2.1. Structural Description. Crystal Structure of 1. Compound 1 was synthesized by a one-step hydrothemal B
DOI: 10.1021/acs.inorgchem.5b02196 Inorg. Chem. XXXX, XXX, XXX−XXX
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Inorganic Chemistry 2.2.2. Detonation Properties of 1. Density functional theory was employed to compute the energy of detonation (ΔEdet; Table S1), from which ΔHdet was estimated by using a linear correlation equation (ΔHdet = 1.127ΔEdet + 0.046; r = 0.968).13a The complete detonation reaction of 1 is described as eq 1. Co5C14 H 21N37 → 5Co + 14C + 7NH3 + 15N2
(1)
The heat of detonation (ΔHdet) is calculated to be 3.629 kcal g−1. To the best of our knowledge, ΔHdet of 1 bears comparison with the largest value of the known energetic MOF, ATRZ-1 (3.618 kcal g−1)14 (Table 1) and is much higher than those of traditional explosives, such as trinitrotoluene (TNT; about 0.897 kcal g−1) and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX; about 1.386 kcal g−1).13a The high heat of detonation is probably attributed to the high nitrogen content and rigid 3D framework. The detonation velocity (D) and pressure (P) are particularly vital parameters of the detonation characteristics of energetic materials. The Kamlet−Jacbos36 equations (see the Supporting Information) reported previously were used to estimate the values of D and P for 1. D and P are calculated respectively as 8.749 km s−1 and 34.32 GPa, which have an advantage compared with those reported for the energetic MOFs, as shown in Table 1. To test the safety of the compound, the impact sensitivity, friction sensitivity, and electrostatic discharge sensitivity were investigated. The impact sensitivity value of 1 exceeds 140 cm (>40 J), which is higher than that of TNT (15 J),13a RDX (7.5 J),13a and ATRZ-1 (22.5 J).14 No friction sensitivity is observed up to 36 kg (360 N) for 1. Additionally, like most energetic MOFs, 1 is more insensitive to electrostatic discharge than TNT and RDX. In a word, the compound is very insensitive to external stimuli because of its intricate 3D structure. Detailed comparisons of the key parameters between 1 and common energetic materials are listed in Table 1. 2.2.3. Nonisothermal Kinetic Analysis of 1. The thermokinetic parameters of the exothermal process for 1 were determined by both the Kissinger9b and Ozawa−Doyle9c,d methods. As shown in Table S2, the Ea value derived from the average of Ek and E0 is calculated as 160.072 kJ mol−1, which shows that the exothermic process cannot readily proceed. The Arrhenius equations can be expressed as follows: ln k = 11.389 − 160.072 × 103/RT, which can be used to reckon the rate constant of the thermal decomposition stage of compound 1. 2.3. Magnetic Properties. On the basis of the pentanuclear CoII unit coupled simultaneously with 3-atrz and azido bridges, magnetic measurements have been carried out on polycrystalline samples of compound 1, and the phase purity of the bulk materials is confirmed by PXRD (Figure S1). The temperature dependence of the magnetic susceptibility of compound 1 is investigated in the temperature range of 2−300 K (Figure 2). The room temperature χMT value of 12.04 cm3 K mol−1 per Co5 unit is higher than the expected spin-only value for five isolated CoII ions (9.375 cm3 K mol−1, S = 3/2, and g = 2.0), which is attributed to an unquenched orbital contribution derived from the high-spin CoII centers in the octahedral geometry.37,38 As the temperature decreases from room temperature, χMT declines very slowly down to about 105 K, after which the value decreases rapidly until a minimum value of 7.13 cm3 mol−1 K at ∼25 K, and then abruptly increases to a sharp maximum of 48.69 emu K mol−1 at 12 K, after which it drops rapidly until 2
Figure 2. Temperature dependence of χMT under an applied dc fields of 1 kOe. Inset: χMT minima position in the inset.
K. Such a minimum indicates the appearance of ferromagneticlike interactions, which likely takes place within the linear trimeric clusters. Simultaneously, when the temperature is decreased, the χM value first increases smoothly, then rises abruptly in the region of 25−12 K with values up to 4.63 cm3 mol−1, and finally falls slightly upon further cooling. The χM value at 2 K is 4.41 cm3 mol−1 for 1. The χM−1 versus T curve above 30 K follows the Curie−Weiss law with C = 13.04 cm3 K mol−1 and θ = −25.95 K for 1 (Figure S2). The large negative Weiss constants (θ) and initial decrease of χMT could be a result of the synergetic operation of the spin−orbit coupling of CoII ions, ligand-field effects, and antiferromagnetic (AF) coupling between adjacent CoII ions through the end-on azide and 3-atrz mixed bridges. However, the steep rises in the χM and χMT values at low temperature clearly demonstrate the emergence of spontaneous magnetization. This behavior could be caused by weak ferromagnetism in the AF system, resulting from spin canting (also called “canted antiferromagnetism”):39 the AF-coupled spins from different sublattices are not perfectly antiparallel but canted to each other, and the produced net moments are correlated in a ferromagnetic-like fashion and bloom into long-range ordering below the critical temperature. However, magnetostructural comparisons with previous compounds containing similar bridges indicate that double (μ-1,1N3)(μ-N,N-tetrazole)29 and triple (μ-1,1-N3)bis(μ-N,N-tetrazole) transmit ferromagnetic interactions,40 while the μ-1,1azide bridges, whether double or single,41 and the μ-NCNtetrazole bridges induce AF interactions between CoII ions.42 Therefore, the ferrimagnetic-like behavior of 1 can be suggested to arise from competitive ferromagnetic and AF coupling between CoII ions.43 In order to explore the low-temperature magnetic behavior of 1, field-cooled (FC) and zero-field-cooled (ZFC) magnetization experiments were performed under a 10 Oe applied field (Figure 3). The FC curve increases rapidly below 15 K and approaches a saturation value at 10 K, suggesting the occurrence of spontaneous magnetization and spin-canted AF ordering. ZFC magnetization undergoes a rise to a maximum with a peak temperature of 14 K and drops sharply to a minimum below 10 K. The two curves diverge at about 16 K, indicating magnetlike irreversibility and the occurrence of longrange ordering within the material. The critical temperature Tc value is assessed to be 16 K by observation of the ZFC and FC plots. Further evidence was provided by the specific heatcapacity measurements (Figure 4). The curve under zero field affords an explicit λ-type anomaly about 16 K, confirming the C
DOI: 10.1021/acs.inorgchem.5b02196 Inorg. Chem. XXXX, XXX, XXX−XXX
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Inorganic Chemistry
2.4 Nβ, far below the common saturation value of five CoII centers (at 2.5 K, the effective spin is S = 1/2), exhibiting the existence of large anisotropy and AF interaction. The initial magnetization is almost linear in the field until it saturates at ca. 0.0925 Nβ and then increases gradually to 2.4 Nβ at 50 kOe. The latter values are similar to a fully aligned moment of 2.3 Nβ. The behavior can be regarded as a canted antiferromagnet with a canting angle estimated from sin−1(0.0925/2.3) of 2.3°. The temperature dependence of the alternating-current susceptibility of 1 was measured at frequencies of 1, 10, 33, 100, 333, and 1000 Hz. As can be seen from Figure 6, a strong
Figure 3. FC and ZFC plots for compound 1.
existence of a 3D long-range ordering state due to intermolecular exchanges.
Figure 6. χ′M and χ″M versus T plots for 1.
out-of-phase signal appeared in the χ″M versus T plot at about 15 K, both in-phase χ′M and out-of-phase χ″M signals are weakly frequency-dependent, and the temperature of the peaks Tp in χ″M moves from 13.52 to 13.93 K with a frequency from 1 to 1000 Hz. The shift parameter Φ = (ΔTP/TP)/Δ(log f) = 0.01 deviates severely from the typical range (0.1 ≤ Φ ≤ 0.3) of the superparamagnetic materials.44,45 The extremely short relaxation time could be predicted because of the tiny frequency dependence on the out-of-phase χ″M curves. As a tentative explanation, we presume that the dynamic behavior arises from the restricted movement of domain walls upon approaching Tc. Further studies are needed to clarify the exact mechanism. Magnetization hysteresis is another important characteristic of the magnetic bistability of a magnet, so the direct-current (dc) magnetization is measured at 2.5, 4, 10, and 15 K within ±10 kOe (Figure 7). At 2.5 K, the compound exhibits a hysteresis loop that shows the double sigmoidal shape typical of metamagnetism, depending on the anisotropy of the CoII ion. Remarkably, the compound behaves as a hard magnet with a large coercive field of 5.5 kOe and a remnant magnetization of 0.74 Nβ. To the best of our knowledge, a few cobalt(II)
Figure 4. Specific heat measured under zero dc field for 1. Inset: Data below 25 K.
As shown in Figure 5, the isothermal field-dependent magnetization M(H) values at 2.5 K and fields up to 50 kOe
Figure 5. Field dependence of M of 1 at 2.5 K. Inset: magnetization versus H plots in fields of 0−15 kOe.
are measured for 1. The metamagnetism is performed by the low-field sigmoidal shape of the initial magnetization curve (Figure 5, inset), from which the critical field is estimated to be 3 kOe. The magnetization curve increases linearly under very low field, subsequently climbs up quickly until 10 kOe, and then rises up gradually to 50 kOe with an effective moment of
Figure 7. Hysteresis loop of 1 at 2.5, 4, 10, and 15 K. D
DOI: 10.1021/acs.inorgchem.5b02196 Inorg. Chem. XXXX, XXX, XXX−XXX
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ACKNOWLEDGMENTS We gratefully acknowledge financial support from the National Natural Science Foundation of China (Grants 21373162, 21203149, 21127004, 21173168, and 21463020) and Nature Science Foundation of Shaanxi Province (Grants 11JS110, FF10091, and SJ08B09).
compounds have previously been reported to show such a large coercivity for 1.24,28,46 A notable feature common to the compound is that the hysteresis loop exhibits two reproducible steps when the field is swept from one end to the other end of the loop. The first step occurs in a narrow range (±100 Oe) across zero field, whereas the second step crosses the M = 0 axis and corresponds to the reversal of magnetization, with the critical fields (≈±8.0 kOe) being close to the coercive fields. The step size (the magnitude of magnetization decrease) of the first step for 1 is from 0.78 to 0.72 Nβ. Hysteresis loops were also obtained at 4, 10, and 15 K for 1 (Figure 7). At 4 K, the metamagnetic transition and two steps in the illustrations are still present. The coercive field is weaker (3.5 kOe) than that at 2 K, although the remnant magnetization (0.75 Nβ) is comparable. At 10 K, the steps in the hysteresis loop still exist but are indiscernible. The coercive field is also much smaller (220 Oe) than those at 2 and 4 K; similarly, the remnant magnetization (0.72 Nβ) remains the same as before, while at 15 K, the steps in the hysteresis loop disappear, and the coercive field and remnant magnetization are negligibly small. In this sense, as the temperature is elevated, the hysteresis loop drastically diminishes and almost disappears, indicating that the material is transformed from a hard to a very soft magnet.
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ASSOCIATED CONTENT
S Supporting Information *
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.5b02196. Details of PXRD curves, magnetic exchanges of CoII cations in compound 1, physical measurements, preparation for 1, heat of detonation, calculated parameters used in the detonation reaction, detonation performances, sensitivity, nonisothermal kinetic analysis, and peak temperatures of the exothermic stage at different heating rates and kinetic parameters (PDF) X-ray crystallographic data in CIF format (CIF)
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REFERENCES
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3. CONCLUSIONS In summary, a 3D Co II-MOF has been continuously investigated in order to explore the multifunctionality in energetic and magnetic fields. The energetic compound displays the combination of excellent detonation characteristics and favorable safety depending on the high nitrogen content (N = 51.68%) and rigid structural framework. At low temperature, magnetic investigation reveals that the compound shows weakly slow relaxation, acting as a hard magnet with a large coercivity of 5.5 kOe at 2.5 K. It indicates the AF ordering below 16 K. The finding in this work has exemplified an effective attempt for developing advanced magnetoenergetic materials.
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Notes
The authors declare no competing financial interest. E
DOI: 10.1021/acs.inorgchem.5b02196 Inorg. Chem. XXXX, XXX, XXX−XXX
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DOI: 10.1021/acs.inorgchem.5b02196 Inorg. Chem. XXXX, XXX, XXX−XXX
