Gem-dinitromethyl-substituted Energetic Metal–Organic Framework based on 1,2,3-Triazole from in situ Controllable Synthesis

Article abstract of DOI:10.1002/asia.201800722

Synthesizing energetic metal–organic frameworks at ambient temperature and pressure has been always a challenge in the research area of energetic materials. In this work, through in situ controllable synthesis, energetic metal–organic framework gem-dinitromethyl-substituted dipotassium 4,5-bis(dinitromethyl)-1,2,3-triazole with a “cage-like” crystal packing was obtained and characterized. Most importantly, for the first time, we found that it could be successfully afforded with a catalytic effect of trifluoroacetic acid. This new compound exhibited its high density (2.04 g cm^?3) at ambient temperature, superior detonation velocity (8715 m s^?1) to that of lead azide (5877 m s^?1) and comparable to that of RDX (8748 m s^?1). Its detonation products are mainly N₂ (48.1 %), suggesting it is also a green energetic material. The above-mentioned performance indicates its potential applications in detonator devices as lead-free primary explosive.

Full text of DOI:10.1002/asia.201800722

CHEMISTRY
AN ASIAN JOURNAL
www.chemasianj.org
Accepted Article
Title: Gem-dinitromethyl substituted energetic metal-organic framework
based on 1,2,3-triazole from in-situ controllable synthesis
Authors: Hao Gu, Qing Ma, Shiliang Huang, Zhenqi Zhang, Qi Zhang,
Guangbin Cheng, Hongwei Yang, and Guijuan Fan
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: Chem. Asian J. 10.1002/asia.201800722
Link to VoR: http://dx.doi.org/10.1002/asia.201800722
A Journal of
A sister journal of Angewandte Chemie
and Chemistry – A European Journal

Chemistry - An Asian Journal
10.1002/asia.201800722
COMMUNICATION
Gem-dinitromethyl substituted energetic metal-organic
framework based on 1,2,3-triazole from in-situ controllable
synthesis
ab
a
a
a
a
b
Hao Gu,
‡
Qing Ma,
‡
Shiliang Huang, Zhenqi Zhang, Qi Zhang, Guangbin Cheng, Hongwei
Yang,* and Guijuan Fan*a
b
Abstract: Synthesizing energetic metal-organic frameworks at
ambient temperature and pressure has been always a challenge in
the research area of energetic materials. In this work, through in-situ
controllable synthesis, energetic metal-organic framework gem-
dinitromethyl substituted dipotassium 4,5-bis(dinitromethyl)-1,2,3-
triazole with “cage-like” crystal packing was obtained and
characterized. Most importantly, for the first time we found that it could
be successfully afforded with the catalytic effect of trifluoroacetic acid.
attractive precursor, 1,2,3-triazole possesses the relatively high
heat of formation (HOF) as well as multiple substituting positions
among azole frameworks in comparison to tetrazole[7] and
pentazole.[8] On the other hand, the correlation between N-
heterocyclic frameworks with gem-dinitromethyl group and their
corresponding synthesis difficulty was given in Scheme 1. So far,
gem-dinitromethyl substituted mono-ring energetic frameworks
with 1,3,4-oxadiazole, 1,2,4-triazole and furoxan have been
released in rather recent years.[2b,9,10] In addition to the previously
mentioned structures, gem-dinitromethyl substituted 1,2,3-
triazole has not been synthesized yet. Considering the
remarkably high HOF of 1,2,3-triazole (calculated by G2 abinitio
-
3
This new compound exhibited its high density (2.04 g cm ) at ambient
-
1
temperature, superior detonation velocity (8715 m s ) to that of lead
-1
-1
azide (5877 m s ) and comparable to that of RDX (8748 m s ). Its
detonation products are mainly N (48.1 %), suggesting it is also a
2
-
1
method at 240 kJ mol ), it is necessarily worthy of overcoming its
synthesis difficulty. Meanwhile, judicious combination of other
energetic functionalized groups with 1,2,3-triazole is favorable for
maintaining its high HOF in the whole molecule.
green energetic material. The above-mentioned performance
indicates its potential applications in detonator devices as lead-free
primary explosive.
Lead azide is a famous primary explosive, which has been widely
used in civil and military detonator because of its cheap
manufacture. However, in the applications of lead azide lead
contamination is always an important issue which mainly destroys
the human digestive, hematologic and nervous systems.[1] During
the past decades, many “green” candidates have been
discovered for the substitution of lead azide. Among them, the
majority of reported candidates as green primary explosives have
drawn much attention, such as potassium 1,1’-dinitramino-5,5’-
bistetrazolate (K
furoxanate (K BDNMF) and potassium 4,4’-bis(dinitromethyl)-
,3’-azofurazanate (K
BDNMAF).[2] A growing interest in new
2
DNABT), potassium 4,5-bis(dinitromethyl)-
2
3
2
energetic materials featuring gem-dinitro- and fluorodinitro-
explosophore groups emerged and also played a significant role
in the design and construction of high energy density materials,[
which also influenced greatly the development of energetic metal-
organic frameworks.[5] After Shreeve et al synthesized the first
potassium-based metal-organic framework featuring gem-
dinitromethyl,[2c] Lu et al reported another similar structure via
silver(I) ions coordinating with gem-dinitromethyl groups and their
3,4]
self-assembly characteristics.[6] As a N-N-N (N
3
) backbone and
Scheme 1. Evolvement of gem-dinitromethyl substituted mono-ring N-
heterocyclic frameworks with the increase of their individual HOF.
[
[
a]
b]
Dr. H. Gao, Dr. Q. Ma, Dr. S. Huang, Dr. Z. Zhang, Dr. Q. Zhang,
Prof. G. Fan
Department of Energetic Materials
In addition to other azole-frameworks such 1,2,4-triazole and
tetrazole, 1,2,3-triazole has relatively high regioselectivity, which
has been revealed in its previous reactions of N-alkylation and N-
amination.[11] In a continuing effort to seek more functionalized
gem-dinitromethyl energetic materials, in this work we aimed to
design and construct 1,2,3-triazole based gem-dinitromethyl
specific molecules. To the best of our knowledge, no methods for
the successful introduction of the gem-dinitromethyl group into
carbon positions in 1,2,3-triazole mono-ring have been reported.
As shown in Scheme 2, 4,5-dicyano-2H-1,2,3-triazole (1) was
prepared by cyclization of diaminomaleodinitrile and then 2H-
Institute of Chemical Materials, China Academy of Engineering
Physics (CAEP), Mianyang, 621900, China
E-mail: fanguijuan@caep.cn
Dr. H. Gao, Prof. G. Cheng, Prof. H. Yang
School of Chemical Engineering
Nanjing University of Science and Technology
Nanjing, 210094, China
Dr. H. Gao and Dr. Q. Ma contributed equally to this work.
‡
Supporting information for this article is given via a link at the end of
the document.
This article is protected by copyright. All rights reserved.

Chemistry - An Asian Journal
10.1002/asia.201800722
COMMUNICATION
1
1
,2,3-triazole-4,5-bis(carboxamidoxime) (2)[12] as well as 2H-
,2,3-triazole-4,5-bis(carboxoxim dichloride) (3)[13] were also
with eight molecular moieties in the unit cell and a density of 2.040
g cm-3 at 296K. During nitration or nucleophilic substitution
reactions, H-proton usually transferred from 2-substituted position
to 1- or 3- substituted positions, which have been reported
recently.[14,15] In this work, H-proton transfers in compound 5 and
6 but settles in the 2-substituted position of compound 8, which
may attribute to the symmetry of two gem-dinitromethyl groups. In
compound 5, the methyl formate group is coplanar with the plane
of 1,2,3-triazole (∠N1-C1-C4-O3=0o) while the gem-
dinitromethyl group twisted out of the plane of 1,2,3-triazole with
synthesized as key intermediates being used in the next steps.
Unlike the other synthesis of gem-dinitromethyl compounds,[
in the initial attempt to get the target compound, nitration of 3 in
2b,2c]
3
100% HNO /trifluoroacetic anhydride (TFAA) resulted in
compound 4 as a colorless oil. Then reduction of 4 in the
presence of potassium iodide and methanol led to potassium 4-
dinitromethyl-5-methylformate-1,2,3-triazolate (5). To investigate
the influence of aprotic solvent on the reduction reaction, we
replaced anhydrous methanol (protic solvent) with anhydrous
acetonitrile in the reduction of 4 and afforded another new
o
a large torsion angle ( ∠ N3-C2-C3-N4=-93.53(18) ). Though
formic-yl replaces methyl formate-yl in compound 6, it shares the
similar structural characteristics with compound 5 except that H-
proton transfers from neighboring gem-dinitromethyl group to
carboxyl group nearby. Because the existence of water molecule
and anionic component in formic acid structure, compound 6
represents different intermolecular interaction. The strong and
quite directed O7–H7A•••O5 (D•••A: 2.869(4) Å; D–H•••A: 161(4)o,
symmetry code: -x+1, y-1/2, -z+3/2) and N1–H1•••O5’ (D•••A:
compound
dipotassium
4-dinitromethyl-5-carboxyl-1,2,3-
triazolate (6). We hypothesize that compound 3 behaves different
reactivity in its 4- and 5-position which thereby has remarkable
influence on the formation of final nitration product.
H
N
H
N
H
N
H
2
N
NH
2
NaNO
2
,HCl
NH
2
OH·H
2
O
NaNO2
N
N
N
N
N
N
NC
CN
H
2
O
H
2
O,80°C,reflux
N
N
2
HCl , H O
N
N
0o
C
NC
CN
RT
HO NH2 NH OH
0-5 C
o
HO Cl
Cl OH
o
2
2.639(4) Å; D–H•••A: 167(4) , symmetry code: x, -y+3/2, z+1/2)
1
3
2
hydrogen bond (H-bond) result in the formation of multiple H-bond
chains. Meanwhile, the central ions K1 and K2 in 6 show different
coordination features. In other words, K1 is coordinated with both
O1 and O3 atoms in gem-dinitromethyl group while K2 is
coordinated with O6 atom in formic-yl as well as O7 atom in water.
H
N
N
HN
N
1
00%HNO
3
N
N
KI
3
O
2
O N
TFAA,CHCl
RT
3
O
2
N
COOH
3
CH OH, RT
0o
Cl NO
NO
2
OCH
3
C
2
K
4
5
CH3CN,
N
R
N
NH
2K
T
2
O N
COO
NO
2
6
H
H
N
N
N
N
1
00%HNO
3
N
N
2K
NO
NO
KI
3
NO
2
2
O N
O
2
N
2
TFA,TFAA,CHCl
RT
3
Cl
Cl CH OH, RT
3
0o
NO
2
NO
2
NO
2
2
C
7
8
Scheme 2. Synthesis of derivatives 4–8 based on
3 with or without
trifluoroacetic acid as a catalyst and different solution effects in the reduction by
iodine potassium.
Subsequently, we chose adding amount of trifluoroacetic acid
(TFA) in the nitration system. To our surprise, major product 7 was
obtained through gradient column chromatography (petroleum
ether: ethyl acetate from 5:1 to 1:1), which implied that the role of
TFA played as an efficient catalyst after the formation of 7. It was
also found that the reaction time and usage quantity of TFA
3
(Comp.3: TFA: TFAA: 100%HNO =6: 8.8: 8.8: 5, in volume) were
significant for affording considerable yield of dipotassium 4,5-
bis(dinitromethyl)-1,2,3-triazolate (8) (detailed reaction conditions
can be found in Table S1).
Crystals of compounds 5, 6 and 8 were obtained by slow
evaporation from aqueous solutions of the corresponding
compounds at room temperature, as pale yellow blocks or plates.
All compounds have been fully characterized by X-ray
crystallography. Their crystal structures and crystal packing were
shown in Figure 1-2 and the crystallographic data and refinement
details, selected bond lengths, angles are given in Table S2-12.
Compound 5 crystallizes in the orthorhombic space group P nma
with four molecular moieties in the unit cell and a density of 1.729
Figure 1. (a) Thermal ellipsoid plot (50%) and labelling scheme of 5. (b) Thermal
ellipsoid plot (50%) and labelling scheme of 6•H O.
2
In comparison with complexes 5 and 6, different coordination
forms were seen in compound 8. As illustrated in Figure 2a, K ions
coordinate with N atoms in both sides of 1,2,3-triazole framework
due to its high structural symmetry. Strong intermolecular H-bond
interaction was found in Figure 2b with 2.15–2.45 Å length.
Because the existence of H-bond interaction as well as O atoms
and N atoms both coordinating with K ions, Figure 2c shows a 3D
framework of compound 8 which represents a rarely seen “cage-
g cm-3 at 293K. Compound 6•H
space group P2
/c with a density of 2.145 g cm-3 at 130K.
Compound 8 crystallizes in the orthorhombic space group P nnm
2
O crystallizes in the monoclinic
1
This article is protected by copyright. All rights reserved.

Chemistry - An Asian Journal
10.1002/asia.201800722
COMMUNICATION
orange and red color indicate organic framework, metal ion and K-O bond,
respectively.
like” crystal packing in 1,2,3-traizole except for the previously
described beetle-like 3D network by S. Chen et al. [5b] Accordingly,
two molecules could be assemble into a fused-ring like framework
similar as benzo[1,2-d:4,5-d’]bistriazole (Figure S1).
The molecule 8 has two possible orientations in its unit cell
(Figure S1). Due to this disorder, the molecule 8 can arrange
in a queue in two different ways along the c-axis and
consequently the neighbouring queues can be parallel or
antiparallel, as shown in Figure 3a and Figure 3c. Each K+
cation was coordinated by three 8 molecules through seven O
atoms and one N atom. By sharing two O atoms, a K
dimer was formed. Because of the different arrangement of 8
molecules, the K 10 dimer has two different configurations
2 2 10
N O
2 2
N O
+
with the two K centers symmetrically related by inverse center
or 2-fold ration axis, as shown in Figure 3b.
Figure 3. Two different arrangement of 8 molecules with neighbouring
queues (a) parallel or (c) antiparallel, which results (b) two configuration s of
K N O10 dimer.
2 2
The powdered samples of compound 8 displayed irregular
flake morphology and the particle size were in the range of 20–50
μm with partially agglomeration (Figure S8). Different from twice
o
o
o
decomposition in 5 (Tp1:131 C, Tp2:181 C) and 6 (Tp1:133 C, Tp2
:
o
2
23 C) (Figure S9 and S10), 8 shows its onset decomposition
o
temperature (T
o
d
) at 120 C and decomposition peak (T
p
) at 131
o
-1
C with the heating rate of 5 C min (Figure S11). The detonation
performance were evaluated by EXPLO5 V6.02.[ Compound 8
16]
-
1
shows its theoretical detonation velocity at 8715 m s , which is
superior to that of commercial primary explosive 2-diazonium-4,6-
-
1
-1
3 2
dinitrophenol (DDNP) (7651 m s ), Pb(N ) (5877 m s ) and
-
1
comparable to that of RDX (8748 m s ). Its detonation pressure
is 28.3 GPa, which is superior to that of DDNP (23.8 GPa), but
slightly lower than that of Pb(N )
3 2
(33.4 Gpa).[1c,2b,2c] Its measured
impact sensitivity (IS) is 1 J and friction sensitivity (FS) is 60 N by
using standard BAM drop hammer as well as friction tester, which
are superior to those of DDNP (IS: 1 J, FS: 5 N).[ 1c,2b,2c] Though
its impact sensitivity is slightly sensitive comparing with that of
Pb(N
to that of Pb(N
products are mainly N
potassium 4,5-bis(dinitromethyl)furoxanate (less than 25%).[
Other products are O (g, 17.1%), CO (g, 13.8%), K CO (s,
3.8%) and H O (g, 6.9%), suggesting as-synthesized energetic
)
3 2
(2.5–4J), its friction sensitivity is more insensitive referred
(0.1–1N). Its predicted detonation gasous
(g, 48.1%) which is higher than that of
3 2
)
2
2b]
2
2
2
3
1
2
metal-organic framework is a green energetic material.
Figure 2. (a) Thermal ellipsoid plot (50%) and labelling scheme of 8. (b)
Intermolecular hydrogen bonding interaction of 8. Dashed lines indicate
strong hydrogen bond. (c) The “cage-like” 3D-framework diagram of 8. Blue,
Table 2. Energetic and physical properties of 8.
This article is protected by copyright. All rights reserved.

Chemistry - An Asian Journal
10.1002/asia.201800722
COMMUNICATION
Ed. 2014, 53, 8172–8175; Angew. Chem. 2014, 126, 8311–8314; b)
C. He, J. M. Shreeve, Angew. Chem. Int. Ed. 2016, 55, 772–775;
Angew. Chem. 2016, 128, 782–785; c) Y. Tang, C. He, L. A.
Mitchell, D. A. Parrish, J. M. Shreeve, Angew. Chem. Int. Ed. 2016, 55,
5565–5567; Angew. Chem. 2016, 128, 5655–5657.
8
DDNP
1.73
–60.9
26.7
64.7
7651
23.8
139
157
1
Pb(N
3 2
)
-
3 [a]
ρ (g cm )
2.04
+15.9
27.8
64.0
8715
28.3
-135
131
1
4.80
Ω (%)[b]
–11.0
28.9
28.9
5877
33.4
450.1
315
[
3]
a) J. Zhang, Q. Zhang, T. T. Vo, D. A. Parrish, J. M. Shreeve, J. Am.
Chem. Soc. 2015, 137, 1697–1704; b) X. X. Zhao, S. H. Li, Y. Wang,
Y. C. Li, F. Q. Zhao, S. P. Pang, J. Mater. Chem. A 2016, 4, 5495–
N (%)
N+O (%)
5504; c) S. Dharavath, J. Zhang, G. H. Imler, D. A. Parrish, J. M.
Shreeve, J. Mater. Chem. A 2017, 5, 4785–4790; d) Y. Li, H. Huang,
Y. Shi, J. Yang, R. Pan, X. Lin, Chem. Eur. J. 2017, 23, 7353–7360;
e) Q. Ma, H. Gu, J. Huang, F. Nie, G. Fan, L. Liao, W. Yang, New
J. Chem. 2018, 42, 2376–2380; f) Q. Ma, H. Gu, J. Huang, D. Liu, J. Li,
G. Fan, Propellants, Explos., Pyrotech. 2018, 43, 90–95.
-
1 [c]
D (m s )
P (GPa)[d]
-
1 [e]
f
ΔH (kJ mol )
[
4]
a) M. A. Kettner, K. Karaghiosoff, T. M. Klapötke, M. Sućeska, S.
Wunder, Chem. Eur. J. 2014, 20, 1–11; b) R. Haiges, K. O.
T
dec (oC)[f]
Christe, Dalton Trans. 2015, 44, 10166–10176; c) D. E. Chavez, D. A.
Parrish, L. Mitchell, Angew. Chem. Int. Ed. 2016, 55, 8666–8669;
Angew. Chem. 2016, 128, 8808–8811; d) A. B. Sheremetev, V. L.
Korolev, A. A. Potemkin, N. S. Aleksandrova, N. V. Palysaeva, T. H.
Hoang, V. P. Sinditskii, K. Yu. Suponitsky, Asian J. Org. Chem. 2016,
IS (J)[g]
2.5-4
0.1-1
FS (N)[h]
60
5
[
a] Density measured by single-crystal X-ray diffraction and converted into
5
, 1388–1397; e) Q. Ma, Z. Lu, L. Liao, J. Huang, D. Liu, J. Li, G. Fan,
room-temperature values; [b] Oxygen balance; [c] Calculated detonation
velocity; [d] Calculated detonation pressure; [e] Heat of formation; [f]
RSC Adv. 2017, 7, 38844–38852; f) Q. Ma, H. Gu, H. Lu, L. Liao, J.
Huang, G. Fan, J. Li, D. Liu, ChemistrySelect 2017, 2, 4567–4571; g)
J. Ma, H. Yang, G. Cheng, New J. Chem. 2017, 41, 12700–12706.
a) S. Li, Y. Wang, C. Qi, X. Zhao, J. Zhang, S. Zhang, S. Pang, Angew.
Chem. Int. Ed. 2013, 52, 14031–14035; Angew. Chem. 2013, 125,
14281–14285; b) Y. Feng, X. Liu, L. Duan, Q. Yang, Q. Wei, G. Xie, S.
Chen, X. Yang, S. Gao, Dalton Trans. 2015, 44, 2333–2339; c) J.
Zhang, Y. Du, K. Dong, H. Su, S. Zhang, S. Li, S. Pang, Chem. Mater.
o
-1
Decomposition temperature measured by DSC/DTA (β=5 C min ); [g]
Impact sensitivity measured by BAM drop-hammer test; [h] Friction
sensitivity measured by a BAM friction tester.
[
5]
In summary, we developed a new in-situ controllable strategy
for successfully synthesizing energetic metal-organic framework
with mono-heterocyclic ring. These first reported frameworks in
different reaction conditions were confirmed by single-crystal X-
ray analysis. It is worth noting that, potassium 4,5-
bis(dinitromethyl)-1,2,3-triazolate (8) has a high crystal density of
2
016, 28, 1472–1480; d) S. Zhang, Q. Yang, X. Liu, X. Qu, Q. Wei, G.
Xie, S. Chen, S. Gao, Coordin. Chem. Rev. 2016, 307, 292–312; e) Y.
Zhang, S. Zhang, L. Sun, Q. Yang, J. Han, Q. Wei, G. Xie, S. Chen, S.
Gao, Chem. Commun. 2017, 53, 3034–3037.
2
.04 g cm-3 at the room temperature, calculated high detonation
[
[
6]
7]
C. Shen, Y. Liu, Z. Zhu, Y. Xu, M. Lu, Chem. Commun. 2017, 53,
-
1
3 2
velocity (8715 m s ), which is superior to that of Pb(N ) (5877 m
7489–7492.
-
1
-1
s ) and approach that of RDX (8748 m s ). The above-mentioned
performance indicates its potential applications in lead-free
primary explosives as high energy and green energetic material.
a) N. Fischer, D. Fischer, T. M. Klapötke, D. G. Piercey, J. Stierstorfer,
J. Mater. Chem. 2012, 22, 20418–20422; b) T. M. Klapötke, M. Q.
Kurz, R. Scharf, P. C. Schmid, J. Stierstorfer, M. Sućeska,
ChemPlusChem 2015, 80, 97–106; c) D. Izsάk, T. M. Klapötke, C.
Pflüger, Dalton Trans. 2015, 44, 17054–17063; d) D. Fischer, T. M.
Klapötke, M. Reymann, J. Stierstorfer, M. B. R. Völkl, New J. Chem.
Acknowledgements
2015, 39, 1619–1627; e) N. Szimhardt, M. F. Bölter, M. Born, T. M.
Klapötke, J. Stierstorfer, Dalton Trans. 2017, 46, 5033–5040.
This work was supported by the Science Challenge Project
[8]
a) C. Zhang, C. Sun, B. Hu, C. Yu, M. Lu, Science 2017, 355, 374–
376; b) K. O. Christe, Science 2017, 355, 351–353; c) Y. Xu, Q. Wang,
(Grant No. TZ2018004), the NSAF Foundation of National
C. Shen, Q. Lin, P. Wang, M. Lu, Nature 2017, 549, 78–81; d) Y. Xu,
P. Wang, Q. Lin, M. Lu, Dalton Trans. 2017, 46, 14088–14093.
J. Zhang, S. Dharavath, L. A. Mitchell, D. A. Parrish, J. M. Shreeve, J.
Am. Chem. Soc. 2016, 138, 7500–7503.
Natural Science Foundation of China and China Academy of
Engineering Physics (Grant No. U1530262), the National Natural
Science Foundation of China (Grant No. 11402237 and
[
[
[
9]
10] Q. Yu, P. Yin, J. Zhang, C. He, G. H. Imler, D. A. Parrish, J. M.
Shreeve, J. Am. Chem. Soc. 2017, 139, 8816–8819.
11302200) and the Science and Technology Development
Foundation of China Academy of Engineering Physics (Grant
No. 2015B0302055).
11] a) C. He, J. M. Shreeve, Angew. Chem. Int. Ed. 2015, 54, 6260–6264;
Angew. Chem. 2015, 127, 6358–6362; b) C. He, P. Yin, L. A. Mitchell,
D. A. Parrish, J. M. Shreeve, Chem. Commun. 2016, 52, 8123–8126;
c) D. Chand, C. He, J. P. Hooper, L. A. Mitchell, D. A. Parrish, J. M.
Shreeve, Dalton Trans. 2016, 45, 9684–9688.
Keywords: gem-dinitromethyl • energetic metal-organic
framework • 1,2,3-triazole • high energy • green energetic
material
[
[
12]
M.-J. Crawford, K. Karaghiosoff, T. M. Klapötke, F. A. Martin, Inorg.
Chem. 2009, 48, 1731–1743.
13]
A. A. Dippold, D. Izsák, T. M. Klapötke, C. Pflüger, Chem. Eur. J.
2016, 22, 1768–1778.
[
1]
a) T. M. Klapötke, High Energy Density Materials, Springer, Berlin, 2015;
b) P. Pagoria, Propellants Explos. Pyrotech. 2016, 41, 452–469; c) D.
Fischer, J. L. Gottfried, T. M. Klapötke, K. Karaghiosoff, J. Stierstorfer, T.
G. Witkowski, Angew. Chem. Int. Ed. 2016, 55, 16132–16135; Angew.
Chem. 2016, 128, 16366–16369.
[14]
[15]
[16]
D. Izsάk, T. M. Klapötke, C. Pflüger, Dalton Trans. 2015, 44,
17054–17063.
T. M. Klapötke, B. Krumm, C. Pflüger, J. Org. Chem. 2016, 81,
6123–6127.
[
2]
a) D. Fischer, T. M. Klapötke, J. Stierstorfer, Angew. Chem. Int.
M. Sućeska, EXPLO5, version 6.02, 2013.
This article is protected by copyright. All rights reserved.

Chemistry - An Asian Journal
10.1002/asia.201800722
COMMUNICATION
COMMUNICATION
Energetic metal-organic
framework featuring gem-
dinitromethyl moiety and
H. Gu, Q. Ma, S. Huang, Z.
Zhang, Q. Zhang, G. Cheng,
H. Yang*, and G. Fan*
1,2,3-triazole with a “cage-
like” crystal packing was
successfully prepared
through in-situ controllable-
synthesis strategy.
Page 1. – Page 4.
Gem-dinitromethyl
substituted energetic
metal-organic framework
based on 1,2,3-triazole from
in-situ controllable
synthesis
This article is protected by copyright. All rights reserved.