1D energetic metal–organic frameworks assembled with energetic combination of furazan and tetrazole

Article abstract of DOI:10.1016/j.poly.2017.10.019

Two novel 1D Cd(II) energetic MOFs [Cd(NH₂NH₂)(AFT)₂·0.7H₂O]_n (1) and [Cd(ODH)_1.5(AFT)₂·5H₂O]_n (2), combining the advantages of tetrazole-ring and furazan-ring, were successfully synthesized based on 2D energetic MOF [Cd(H₂O)₂(AFT)₂]_n (3, AFT = 4-amino-3-(5-tetrazolate)-furazan, ODH[dbnd]NH₂NHCOCONHNH₂[dbnd]oxalyl-dihydrazide). The crystal structures were determined by single-crystal X-ray diffraction, and fully characterized by elemental analysis and FT-IR spectroscopy. The thermal stability and impact sensitivity were also investigated. For 1, 1D energetic MOF had an outstanding thermal stability (T_p > 300 °C) and insensitivity (IS > 24.5 J). In addition, the non-isothermal kinetics parameters, critical temperature of thermal explosion, entropy of activation, enthalpy of activation and free energy of activation were discussed in detail. For 2, it was revealed that the each Cd(II) cation is located in a unique hepta-coordination environment. Noticeably, tetrazole-ring of AFT group presents typical monodentate coordination mode, and ODH molecule presents typical tridentate and tetradentate coordination modes, featuring a one-dimensional chain structure. Therefore, the reasonable assembly strategy plays a decisive role in energetic properties of MOF-based energetic materials.

Full text of DOI:10.1016/j.poly.2017.10.019

Accepted Manuscript
1
D Energetic Metal–organic Frameworks Assembled with Energetic Combina-
tion of Furazan and Tetrazole
Bi-Dong Wu, Xu-Yang Li, Jie Liang, Xiao-Heng Geng, Hui-Sheng Huang, He
Huang, Jing-Yu Wang, Wu-Hong Hu
PII:
S0277-5387(17)30680-0
https://doi.org/10.1016/j.poly.2017.10.019
POLY 12882
DOI:
Reference:
To appear in:
Polyhedron
Received Date:
Accepted Date:
8 September 2017
12 October 2017
Please cite this article as: B-D. Wu, X-Y. Li, J. Liang, X-H. Geng, H-S. Huang, H. Huang, J-Y. Wang, W-H. Hu,
1
D Energetic Metal–organic Frameworks Assembled with Energetic Combination of Furazan and Tetrazole,
Polyhedron (2017), doi: https://doi.org/10.1016/j.poly.2017.10.019
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1
D Energetic Metal–organic Frameworks Assembled with Energetic Combination of
Furazan and Tetrazole
*
1
1
1
2
3
4
Bi-Dong Wu , Xu-Yang Li , Jie Liang , Xiao-Heng Geng , Hui-Sheng Huang , He Huang ,
1
*3
Jing-Yu Wang , Wu-Hong Hu
1
Shanxi Engineering Technology Research Center for Ultrafine Powder, School of Environment and Safety
Engineering, North University of China, Shanxi 030051, China
2
3
College of Resources and Environmental Engineering, Binzhou University, Binzhou 256603, China
Chongqing Key Laboratory of Inorganic Special Functional Materials, College of Chemistry and Chemical
Engineering, Yangtze Normal University, Chongqing 408100, China
4
Blast Protection Technology Laboratory, the Military Institute, Jiangyang Chemical Limited Company, Jinxi
Group, Taiyuan 030041, China
*
Corresponding author: Dr. B. D. Wu, E-mail: wubidong@nuc.edu.cn; Prof. W. H. Hu, E-mail:
hwh262@126.com
Abstract: Two novel 1D Cd(II) energetic MOFs [Cd(NH NH )(AFT) ∙0.7H O] (
1
) and
), combining the advantages of tetrazole-ring and furazan-ring,
were successfully synthesized based on 2D energetic MOF [Cd(H O) (AFT) ] (3,
2
2
2
2
n
[
Cd(ODH) (AFT) ∙5H O] (2
1.5 2 2 n
2
2
2 n
AFT=4-amino-3-(5-tetrazolate)-furazan, ODH=NH NHCOCONHNH = oxalyl-dihydrazide). The
2
2
crystal structures were determined by single-crystal X-ray diffraction, and fully characterized by
elemental analysis and FT-IR spectroscopy. The thermal stability and impact sensitivity were
o
also investigated. For
1
, 1D energetic MOF had an outstanding thermal stability (T >300 C) and
p
insensitivity (IS>24.5 J). In addition, the non-isothermal kinetics parameters, critical temperature
of thermal explosion, entropy of activation, enthalpy of activation and free energy of activation
were discussed in detail. For 2, it was revealed that the each Cd(II) cation is located in a unique
hepta-coordination environment. Noticeably, tetrazole-ring of AFT group presents typical
monodentate coordination mode, and ODH molecule presents typical tridentate and tetradentate
coordination modes, featuring a one-dimensional chain structure. Therefore, the reasonable
assembly strategy plays a decisive role in energetic properties of MOF-based energetic materials.
Keywords: Tetrazole; Furazan; MOF; Crystal structure; Thermal behaviour
1
/ 14

1
. Introduction
High-energetic metal-organic frameworks (HE-MOFs) have been achieved by the
+
2+
2+
3+
2+
2+
2+
self-assembly of metal ions (such as Ag , Cu , Ni , Co , Co , Zn , Cd , etc) and energetic
bidentate and (or) multidentate ligands, which will significantly influence the designing MOFs
structures and ultimately the energetic properties. By virtue of this strategy, a new class of one-,
two- and three-dimensional (1D, 2D and 3D) energetic MOFs are emerging, which are expected
to possess the desired physical (such as high density, reasonable fluidity) and chemical properties
(such as high thermal stability, high energetic output, low sensitivity and low environmental
impact)[1-12]. Shreeve et al. highlighted the application prospects and development potentials of
HE-MOFs in the field of energetic materials[13, 14]. Physicochemical properties of 37 HE-MOFs
from 1D to 3D, based on various nitrogen-rich energetic ligands, had been summarized by Chen
et al.[1]. It was found that, oxygen-containing energetic groups ameliorate oxygen balance of the
whole system to fully release the energy. Therefore, in regard to the requirements of detonation
-
1
performance and safety, very promising is furazan-ring (185 kJ·mol ) conjugated with tetrazole
-
1
-1
(
200 kJ·mol ), heats of formation of which are more than the 1,2,4-oxadiazole (51·kJ mol ),
-
1
-1
-1
pyrazole (171 kJ·mol ), imidazole (124 kJ·mol ), and 1,2,4-triazole (182 kJ·mol )[15].
Undoubtedly, it is propitious to constructing high-dimensional energetic frameworks with more
outstanding physicochemical properties by 4-amino-3-(5-tetrazolate)-furazan (HAFT). Prof.
Shreeve had reported energetic salts by HAFT, all of which possess relatively high density, acceptable
impact and friction sensitivities, and good detonation pressure and velocity[15]. On the other hand,
3
D
energetic MOF [Ag (BTFOF) ] ·[2(NH )]
assembled with Ag(I) ions and
1
6
9 n
4
n
4
,4′-oxybis[3,3′-(1H-5-tetrazol)]furazan (H BTFOF) had an outstanding insensitivity (IS>40J), an
2
−
1
ultrahigh detonation pressure of 65.29 GPa and a detonation velocity of 11.81 km·s [2].
Therefore, synthesizing the ligands above is a feasible and promising route to construct HE-MOFs.
Herein, we had reported a 2D energetic MOF [Cd(H O) (AFT) ] (3)[5]. On this basis, we report
2
2
2 n
two 1D energetic MOFs [Cd(NH NH )(AFT) ∙0.7H O] (1) and [Cd(ODH) (AFT) ∙5H O] (2,
2
2
2
2
n
1.5
2
2
n
ODH=NH NHCOCONHNH = oxalyl-dihydrazide) by replace coordination water molecules of 3, which
2
2
of synthesis, crystal structures, the thermal decomposition mechanism and explosive performance
were studied in the present work.
2
. Experimental Section
2
.1 Materials and Physical Techniques
All the reagents and solvents were of analytical grade and used without further purification as
commercially obtained. Elemental analyze was performed on a Flash EA 1112 full-automatic trace
element analyzer. The FT-IR spectra was recorded on a PerkinElmer Spectrum 100 infrared spectrometer
2
/ 14

−
1
-1
(
KBr pellets) in the range of 4000~400 cm with a resolution of 4 cm . DSC measurement was carried
by using DSC-131 differential scanning calorimeter (SETARAM).
.2 The synthesis of 1 and 2 was as follows (Scheme 1
2
)
HAFT (20 mmol) was dissolved in distilled water (20 ml), and charged into a glass reactor with
o
a water bath. It was kept under mechanical stirring and heated to the temperature of 60 C.
Cd(NO ) (1 mol/L, 12ml) was added to the HAFT solution during 15 min with continuous
3
2
stirring. Then, acidified hydrazine hydrate (10 mmol) or acidified oxalyl-dihydrazide (15mmol),
dissolved in distilled water (30 ml), was added to the solution during 5 min and keeping for 30 min.
In the end, the solution was cooled to room temperature naturally. Single crystal suitable for X-ray
measurement was obtained by evaporation of the mother liquor at room temperature for one week.
[
Cd(NH NH )(AFT) ∙0.7H O] (1): Yield: 50% (based on AFT). CdN C H O (461.35): calcd. C
2 2 2 2 n 16 6 9.4 2.7
1
1
5.62, H 2.05, N 48.59; found C 15.72, H 2.23, N 48.52. IR (KBr): 3429, 3327, 3167, 2150, 1784, 1605,
–
1
-1
-1
–1
568 and 768 cm (-NH and -NH ), 1633cm (N=N), 1242cm (-CN), 1153 and 1034 cm
2
(tetrazole-ring).
[
Cd(ODH) (AFT) ∙5H O] (2): Yield: 30% (based on AFT). CdN C H O (673.79): calcd. C 16.04,
1
.5
2
2
n
20
9
13 10
-1
H 1.94, N 41.58; found C 15.86, H 2.34, N 41.32. IR (KBr): 3465, 3335, 3286, 1596 and 784 cm
-1
-1
-1
(
-NH and -NH ), 1732 cm (-C=O), 1249cm (-CN), 1124 and 1066 cm (tetrazole-ring).
2
N
HON
H N
CN
N
N
N
2
H N
2
NH2
CH COOH
NaN3
PbO2
H N
NH
1
)NaNO /CH COOH
2
NC
2
3
CN
N
N
2)NH OH HCl/NaOH
N
N
NH Cl
2
3
4
O
O
HAFT
N
O
Cd(ClO ) or Cd(NO )
3 2 + HAFT
4
2
[Cd(H O) (AFT) ]
2 n
(3)
2
2
Cd(NO ) + NH NH
3
2
2
2
+ HAFT
[Cd(NH NH )(AFT) 0.7H O]
(1)
[Cd(NH NHCOCONHNH ) (AFT) 5H O] (2)
2
2
2
2
n
Cd(NO ) + NH NHCOCONHNH + HAFT
3
2
2
2
2
2 1.5
2
2
n
Scheme 1. Synthesis of HAFT and 1-3.
2
.3 X-ray data collection and structure refinement
The X-ray diffraction data collection was performed with a Rigaku AFC-10/Saturn724 CCD and
+
Bruker APEX-II CCD detector diffractometer with graphite monochromated Mo-Kα radiation. The
structure was solved by direct method using SHELXS-97 and refined by full-matrix least-squares method
2
on F with SHELXL-97. All non-hydrogen atoms were obtained from the difference Fourier map and
2
subjected to anisotropic refinement by full-matrix least squares on F . Detailed information concerning
crystallographic data collection and structure refinement are summarized in Table 1.
Table 1. Crystallographic data and structure determination details.
Compound
1
2
3 [5]
Empirical formula
CdN C H O
CdN C H O
Cd0.25N3.50C1.50H O
1
6
6
9.4 2.7
20
9
13 10
2
3
/ 14

Formula weight
461.35
673.79
113.17
T/K
153.15
100(2)
153(2)
Crystal system
Space group
a/Å
monoclinic
C2/c
triclinic
P-1
monoclinic
P2 /c
1
28.359(8)
7.8563(16)
15.790(3)
90
9.0126(18)
9.982(2)
15.045(3)
87.125(3)
85.468(3)
68.265(3)
1253.0(4)
2
7.857(3)
b/Å
9.409(3)
c/Å
9.046(3)
α/(°)
90
β/(°)
120.72(2)
90
93.560(4)
γ/(°)
90
3
V/Å
3024.3(12)
8
667.4(4)
Z
8
-3
D /(g∙cm )
2.026
1.786
2.252
c
θ/(°)
1.67~27.48
-36~35,-10~9,-20~20
4248
2.20~25.00
-10~5, -11~11, -17~15
6246
3.13 ~31.48
h, k, l
-11~11, -9~13, -12~13
Reflections collections
Independent reflection
S
6408
2200
1.000
3408
4360
1.248
1.058
[
a]
a]
[b]
[c]
R ,wR [I＞2σ(I)]
0.0629, 0.1707
0.0789, 0.2024
1816
0.0587, 0.1422
0.0227, 0.0532
1
2
[
[b]
[c]
R ,wR (all data)
0.0677, 0.1464
0.0307, 0.0570
1
2
F(000)
670
444
CCDC
1523833
1561476
1488809
[
a]
2
2
2
[b]
2
2
2
[c]
2
2
w = 1/[σ (F ) + (0.0852P) + 66.3515P], w = 1/[σ (F ) + (0.0100P) + 14.0000P], w = 1/[σ (F ) +
o
o
o
2
2
2 2
2
1/2
2
2
(
0.0298P) + 0.0000P], wR = [∑w(F –F ) /∑w(F )] , P = (F + 2F )/3.
2 o c o o c
3
Results and Discussion
3
.1 Structure Description
In the previous work, we had reported a 2D energetic MOF [Cd(H O) (AFT) ] (3)[5], which of each
2
2
2 n
two Cd(II) cations can mutual connect through bidentate coordination tetrazole-ring of AFT group, and
form #-shape structure (Supporting Information Figure 1). The crystal structure of 1 belongs to
o
monoclinic, pertains to P2 /c space group, a= 7.857(3) Å, b= 9.409(3) Å, c= 9.046(3) Å, β= 93.560(4)
1
-3
and D =2.252 g∙cm [5]. The purpose is to verify that we can design and synthesis the more complex
c
structures by adding energetic bidentate or multidentate ligands, such as hydrazine and ODH, to replace
two coordination water molecules of 3.
In 1, the crystal structure belongs to monoclinic, pertains to C2/c space group, a= 28.359(8) Å,
o
-3
b= 7.8563(16) Å, c= 15.790(3) Å, β= 120.72(2) and D =2.026 g∙cm (Table 1). There are one
c
cadmium(II) cation, four AFT ligands and two hydrazine molecules from Figure 1. Furazan-ring is
not take part in coordination. Moreover, tetrazole-rings and hydrazine molecules present typical
4
/ 14

bidentate coordination modes, and connect with two cadmium cations, featuring a
one-dimensional chain structure (Figure 2). The six basically equivalent Cd–N bonds are
approximately equal about 2.33-2.45 Å from the Table 2. The bond angles of two contraposition
hydrazine molecules and Cd(II) cation are close to 180° (<N12-Cd1-N11=179.3°), but the bond
angles of two N atoms of contraposition AFT groups and Cd(II) cation are close to 157°
(
<N1A-Cd1-N2=156.8° and <N13-Cd1-N8=157.2°). The nitrogen atoms from two border upon
ligands and Cd(II) cation’s bond angles are all departure from 90°. Therefore, all above data
demonstrate that the each Cd(II) cations of exhibit appreciably distorted–octahedral
configuration. In addition, the distance of two Cd(II) cations (4.08 Å) for is more shorter than
6.53 Å), owing to shortening the distance of two cadmium ions by hydrazine molecule. But has
, which is one reason of lower density. From the
1
1
3
(
1
zero point seven crystal waters compared with
3
packing diagram (Figure 3), intermolecular hydrogen bonds make an important contribution to
extend the structure into a 3D supramolecule and enhance the thermal stability.
Figure 1. Molecular structure of 1, thermal ellipsoids drawn at 30% probability level.
2
+
Figure 2. Coordination mode of Cd in
1
, omit amino-furazan and water molecular for clarity.
/ 14
5

Figure 3. Packing structure of
1 along b-axis of the unit cell.
In
2, the crystal structure belongs to triclinic, pertains to P-1 space group, a= 9.0126(18) Å, b=
o
o
o
-3
9
.982(2) Å, c= 15.045(3) Å, α= 87.125(3) , β= 85.468(3) , γ= 68.265(3) and D =1.786 g∙cm
c
(Table 1). Each Cd(II) cation is located in a hepta-coordination environment with two AFT
groups and three ODH molecules (Figure 4). In addition, Cd(II) cation is related to different
hexadentate coordination mode, such as [Cd(DAT) ](PA) ·4H O (DAT= 1,5-diaminotetrazole,
6
2
2
PA=picrate)[11], [Cd(DAT) ](ClO ) [16], [Cd(DAT) ](NO ) [17], [Cd(DAT) (N ) ] [18],
6
4 2
6
3 2
2
3 2 n
[
Cd(en)(N ) ] (en=ethylenediamine), [Cd(IMI) (N ) ] (IMI=imidazole),
1
and
furazan-ring is also not take part in coordination, and tetrazole-ring presents typical monodentate
coordination mode, which is different in and . In addition, ODH molecule presents typical
3. Noticeably,
3
2 n
2
3 2 n
1
3
tridentate coordination mode and tetradentate coordination mode, and each ODH molecule is also
connected with two cadmium cations (Figure5), featuring a one-dimensional chain structure. For
2
, the distance of two Cd(II) cations (7.43Å) is more than
1 (4.08 Å), resulted tetrazole-ring
presenting single coordination mode. And has more crystal waters, which is also one reason of
2
lower density. The seven basically equivalent Cd–N and Cd–O bonds are approximately equal
about 2.33-2.45 Å from the Table 3. Cd(II) ions and ODH ligands are basically in the same plane,
and the bond angles of two N atoms (contraposition AFT groups) and Cd(II) cation are close to
1
80° (<N1-Cd1-N8=174.2°). Therefore, all above data demonstrate that each Cd(II) cations
exhibit appreciably distorted–decahedral configuration for . From the packing diagram (Figure
), the all furazan-ring and tetrazole-ring are coplanar or in parallel, and the offset face-to-face
π-π stacking distance is about 3.4 Å, resulted a lower impact sensitivity. And intermolecular
2
6
6
/ 14

hydrogen bonds also make an important contribution to extend the structure into a 3D
supramolecule.
Figure 4. Molecular structure of 2, thermal ellipsoids drawn at 50% probability level.
2
+
Figure 5. Coordination mode of Cd and ODH in 2, omit AFT group and water molecular for clarity.
Figure 6. Packing structure of
/ 14
2.
7

Table 2 Selected bond lengths and bond angles for 1.
bond
Cd1-N1
length/ Å
2.337(7)
2.447(7)
2.429(7)
2.350(7)
2.339(7)
2.336(7)
1.456(9)
bond
angle/(°)
156.8(2)
179.3(2)
157.2(2)
85.0(2)
96.6(2)
82.9(2)
76.4(2)
bond
angle/(°)
95.2(2)
84.7(2)
85.1(2)
94.8(2)
116.3(2)
84.6(2)
N1A-Cd1-N2
N12-Cd1-N11
N13-Cd1-N8
N1A-Cd1-N8
N1A-Cd1-N11
N1A-Cd1-N12
N8-Cd1-N2
N11-Cd1-N2
N11-Cd1-N8
N12-Cd1-N2
N12-Cd1-N8
N13-Cd1-N1A
N13-Cd1-N2
Cd1-N2
Cd1-N8
Cd1-N11
Cd1-N12
Cd1-N13
N12-N11A
Table 3. Selected bond lengths and bond angles for 2.
bond
Cd1-N1
Cd1-N8
Cd1-N19
Cd1-N15
Cd1-N18A
Cd1-O3
Cd1-O5
length/ Å
2.303(6)
2.320(6)
2.415(6)
2.450(6)
2.488(5)
2.374(4)
2.383(5)
bond
angle/(°)
174.2(2)
bond
angle/(°)
96.3(2)
N1-Cd1-N8
N15-Cd1-N19
N1-Cd1-O3
N8-Cd1-O3
N1-Cd1-O5
N8-Cd1-O5
O3-Cd1-O5
N1-Cd1-N19
N8-Cd1-N19
O3-Cd1-N19
O5-Cd1-N19
N1-Cd1-N15
N8-Cd1-N15
N15-Cd1-N19
136.4(2)
88.6(2)
88.23(18)
86.00(18)
80.06(19)
104.72(19)
137.17(15)
153.90(18)
68.83(18)
96.2(2)
82.3(2)
136.4(2)
3
.2 Thermal decomposition analysis
In order to investigate the thermal behavior of
calorimetry (DSC) with a linear heating rates of 5, 10, 15 and 20 C∙min in a flowing N
1
and 2, it was analyzed by differential scanning
o
-1
2
-
1
atmosphere with flowing rate 20 ml·min and shown in Figure 7.
In , a melting point could not be observed in the DSC curves, in spite of the presence of
coordination water molecules. The peaks of exothermic decomposition stages were observed at
1
o
o
o
o
o
3
3
1
06.3 C, 320.5 C, 327.0 C and 340.2 C, and onset temperatures were observed at 302.5 C,
o
o
o
08.5 C, 315.7 C and 339.9 C, respectively, corresponding to the linear heating rates of 5, 10,
o
-1
5 and 20 C∙min . Compared with 3, compound 1 has only one exothermic process, and is one
of the few thermally stable energetic materials at temperature higher than 300 °C.
o
o
In
2
, there were two endothermic peaks in the temperature ranges of 50-100 C and 180-200 C,
which are coincident with the loss of all lattice water molecules. Then, the cleavage of amino- and
ODH groups and the breaking of tetrazole and furazan rings are destroyed, so it gets unstable and
begins to decompose. It can be seen from the DSC curve, the decomposition occurs in the
o
temperature range of 220~400 C with one endothermic and two exothermic steps. The peaks of
o
o
o
o
first exothermic decomposition stages were observed at 271.3 C, 287.8 C, 300.0 C and 308.5 C,
o
-1
respectively, corresponding to the linear heating rates of 5, 10, 15 and 20 C∙min . Therefore,
was more unstable than that of
2
1
.
8
/ 14

2
1
2
0
1
5
2
0
1
0
5
1
1
5
0
5
1
00
200
300
400
100
200
300
400
o
o
T/ C
T/ C
o
-1
Figure 7. DSC curves for
.3 Non-isothermal kinetics analysis
It is widely used to determine the Arrhenius Equation for main exothermic peak for 1 with the apparent
1 and 2 with β =5, 10, 15 and 20 C·min in a N atmosphere.
2
3
activation energy E, pre–exponential factor A, linear coefficient R and standard deviation S corresponding
to Kissinger’s method[19], Ozawa’s method[20] and Starink’s method[21], respectively (See Supporting
Information), and was showed in Table 5. So, the Arrhenius equation of 1 can be expressed as follows: (E
3
is the average number): lnk =15.22-117.59×10 /(RT). Then, critical temperature of thermal explosion,
≠
≠
≠
ΔS , ΔH and ΔG of 1 were calculated (See Supporting Information).
Table 5. Peak temperatures of main exothermic and the chemical kinetics parameters for 1.
o
-1
o
Heating rates  / C·min
T
p
/ C
parameters
Kissinger’s method
Ozawa’s method
Starink’s method
-1
5
306.3
320.5
327.0
340.2
E/kJ·mol
113.96
6.61
123.86
-
114.95
-
1
1
2
0
5
0
lgA
R
-0.9802
0.1344
-0.9833
0.1340
-0.9806
0.1344
S
3
.4 Impact Sensitivity Test
The impact sensitivity was determined by fall hammer apparatus. 1 and 2(30 mg) was placed between
two steel poles and was hit by a 5.0 kg drop hammer at a height of 50 cm. The test result showed that the
firing rate was 0% (>24.5 J), which was less sensitive to impact than TNT (15.0 J) and RDX (7.5 J).
The physicochemical properties are tabulated in Table 6.
Table 6. Physicochemical properties of 1, 2 and 3.
≠
≠
≠
N
OB
(%)
Dc
E
T
Tb
ΔS
-1
ΔH
ΔG
IS
p0
Compound
-3
–1
o
o
-1
-1
-1
(
%)
/(g∙cm ) (kJ∙mol ) ( C)
( C)
(J·K ·mol ) (kJ·mol ) (kJ·mol )
(J)
1
2
3
4
4
4
8.59 -52.02
1.58 -36.81
3.30 -45.95
2.026
1.786
2.252
117.59
-
260.0 281.77
-131.52
-
119.43
-
189.55
-
>24.5
>24.5
>24.5
-
-
189.5
296.4 300.23
-0.67
183.46
183.65
9
/ 14

4
. Conclusions
Synthesis
and
characterization
of
two
novel
1D
MOFs
compounds
[
Cd(NH NH )(AFT) ∙0.7H O] (
1
) and [Cd(ODH) (AFT) ∙5H O] (
2
) were reported, which
2
2
2
2
n
1.5
2
2
n
-
3
-3
have 2.026 g cm of crystal density and 48.59% nitrogen content for
crystal density and 48.59% nitrogen content for . They have their respective advantages: (1)
one of the few thermally stable energetic materials at temperature higher than 300 °C; (2)
located in a unique hepta-coordination mode. Therefore, based on 2D MOF compound
obtain 1D MOFs compounds and . There is no doubt that we can also design and synthesis the
D energetic MOFs by adding energetic bidentate ligands (eg. ethylenediamine) or multidentate
1
, and 1.786 g cm of
2
1
2
is
is
3
, we only
1
2
3
ligands (eg. azido-group).
Acknowledgments
The project was supported by Shanxi Province Science Foundation for Youths
(No.201701D221048), the Advantage Disciplines Climbing Plan of Shanxi Province, Science
Foundation of North University of China (2015) and Chongqing Key Laboratory of Inorganic
Special Functional Materials (Yangzte Normal University, No. KFKT201503).
Appendix A. Supplementary data
CCDC 1523833 and 1561476 contains the supplementary crystallographic data for compounds
1
and These data can be obtained free of charge via
2
.
http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from the Cambridge Crystallographic Data
Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail:
deposit@ccdc.cam.ac.uk. Supplementary data associated with this article can be found at
Supporting Information.
References
[
[
[
[
1] S. Zhang, Q. Yang, X. Y. Liu, X. N. Qu, Q. Wei, G. Xie, S. P. Chen, S. L. Gao, Coordin. Chem.
Rev., 2 (2016) 292.
2] X. N. Qu, S. Zhang, B. Z. Wang, Q. Yang, J. Han, Q. Wei, G. Xie, S. P. Chen, Dalton Trans, 16 (2016)
6
968.
3] S. H. Li, Y. Wang, C. Qi, X. X. Zhao, J. C. Zhang, S. W. Zhang, S. P. Pang, Angew. Chem. Int. Edit.,
2 (2013) 14031.
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4] O. S. Bushuyev, G. R. Peterson, P. Brown, A. Maiti, R. H. Gee, B. L. Weeks, L. J. Hope-Weeks,
Chem.-Eur. J., 5 (2013) 1706.
[
[
5] B. D. Wu, J. Liang, J. Y. Wang, C. W. An, Main Group Chem., 1 (2017) 67.
6] B. D. Wu, Y. G. Bi, F. G. Li, L. Yang, Z. N. Zhou, J. G. Zhang, T. L. Zhang, Z. Anorg. Allg. Chem.,
1
(2014) 224.
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[
[
7] B. D. Wu, Z. N. Zhou, F. G. Li, L. Yang, T. L. Zhang, J. G. Zhang, New J. Chem., 3 (2013) 646.
8] B. D. Wu, Y. G. Bi, Z. N. Zhou, L. Yang, J. G. Zhang, T. L. Zhang, J Coord. Chem., 17 (2013) 3014.
9] B. D. Wu, L. Yang, S. W. Wang, T. L. Zhang, J. G. Zhang, Z. N. Zhou, K. B. Yu, Z. Anorg. Allg.
Chem., 3-4 (2011) 450.
[
[
10] L. Yang, B. D. Wu, T. L. Zhang, Z. H. Liu, J. G. Zhang, Propellants Explos. Pyrotech., 6 (2010) 521.
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Egorshin, J Chem. Eng. Data, 9 (2010) 3109.
[
[
[
[
[
[
12] G. H. Tao, B. Twamley, J. M. Shreeve, Inorg. Chem., 20 (2009) 9918.
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14] J. Zhang, J. n. M. Shreeve, Dalton Trans., No.6 (2016) 2363.
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17] J. G. Zhang, J. Y. Li, Y. Zang, Y. J. Shu, T. L. Zhang, L. Yang, P. P. Power, Z. Anorg. Allg. Chem.,
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(2010) 1147.
[
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[
[
18] Z. Tang, J. G. Zhang, Z. H. Liu, T.L. Zhang, L. Yang, X.J. Qiao, J. Mol. Struct., 1-3 (2011) 8.
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11 / 14

Supporting Information
Structure Description
Figure 1. Molecular structure of 3, thermal ellipsoids drawn at 70% probability level (left), and coordination mode of
2+
Cd , omit amino-furazan and water molecular for clarity (right).
Thermal decomposition analysis
3
2
0
1
5
1
0
5
1
00
200
300
400
o
T/ C
o
-1
Figure 2. DSC curves for
3 with β =5, 10, 15 and 20 C·min in a N atmosphere.
2
Non-isothermal kinetics analysis
The equations of Kissinger’s method, Ozawa’s method and Starink’s method are as follows:
s
ln

 T

 

BE RT

C
(1)
–
1
Where T is the peak temperature in K. E is the apparent activation energy in kJ∙mol . R is the gas
–
1
–1
–1
constant (8.314 J∙K ∙mol ). β is the linear heating rate in K∙min . B and C are constant. When
s=2 and B=1, equation (1) is according to Kissinger’s method. When s=0 and B=1.0516, equation
12 / 14

(1) is according to Ozawa’s method. When s=1.8 and B=1.0037, equation (1) is according to
Starink’s method. Based on the exothermic peak temperature measured with four different heating
o
–1
rates of 5, 10, 15 and 20 C∙min , three methods were applied to study the kinetics parameters of
the title compound. From the original data, the apparent activation energy E, pre–exponential
factor A, linear coefficient R and standard deviation S were determined based on the relationship
2
1.8
of ln(β/T ), ln(β/T ) and lnβ to 1/T, corresponding to Kissinger’s method, Starink’s method, and
Ozawa’s method, respectively.
Calculation of critical temperature of thermal explosion, ΔS≠, ΔH≠ and ΔG≠
The value of the peak temperature corresponding to β→0 (T ), the corresponding critical temperature of
0
≠
≠
thermal explosion (T ), entropy of activation (ΔS ), enthalpy of activation (ΔH ), and free energy of
b
≠
activation (ΔG ) were obtained by the following equations (2), where a, b and c are coefficients, k is the
B
–
23
–34
Boltzmann constant (1.381×10 J/K) and h is the Planck constant (6.626×10 J·s).
(2)
1
D
[
Cd(NH NH )(AFT) 0.7H O] (1)
2 2 2 2 n
[
Cd(NH NHCOCONHNH ) (AFT) 5H O] (2)
2D
2
2 1.5
2
2
n
1
D
[
Cd(H O) (AFT) ] (3)
2 2 2 n


Based on 2D MOF compound 3, we only obtain 1D MOFs compounds 1 and 2. 1 is one of the few thermally
stable energetic materials at temperature higher than 300 °C; 2 is located in a unique hepta-coordination
mode.
There is no doubt that we can also design and synthesis the 3D energetic MOFs by adding energetic
13 / 14

bidentate ligands (eg. ethylenediamine) or multidentate ligands (eg. azido-group).
14 / 14