FirePhysChem 2 (2022) 83–139

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FirePhysChem
journal homepage: http://www.keaipublishing.com/cn/journals/firephyschem/

Recent synthetic efforts towards high energy density materials: How to

design high-performance energetic structures?
Jing Zhou a,b, Junlin Zhang b,∗, Bozhou Wang b,∗, Lili Qiu a, Ruoqian Xu b, Aleksei B. Sheremetev c,∗
a
School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081, PR China
b
State Key Laboratory of Fluorine & Nitrogen Chemicals, Xi’an Modern Chemistry Research Institute, Xi’an, 710065, PR China
c
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 119991, Russian Federation

a r t i c l e i n f o a b s t r a c t

Keywords: Energetic material is a very essential company of compounds, widely used in various fields, primarily in the
Explosophoric groups military industry and space technologies. These compounds are unique in that they are capable of instantly de-
High-nitrogen heterocycles composing to release enormous energy. The chemical diversity of energetic organic compounds is constantly
Oxygen-rich group
increasing through the combination of various high-nitrogen frameworks and explosophoric groups, which fol-
Enthalpies of formation
lows the overall trend of increasing interest in their chemistry and applications. The scientific community is
Synthesis
constantly looking for more powerful and less sensitive to external impulses energetic compounds for both mili-
tary and civilian use. Herein, a detailed overview regarding classic and novel explosophoric groups and various
frameworks, as well as a description of the selected synthesis for the target compounds, has been given for the
time period since 2010. The physical properties and performances of benchmark and prospective compounds are
also collected.

1. Introduction recent years, high energy density materials (HEDMs) play a key role
in the development of new generation of high explosives and ingre-
Energetic materials are the key components in weapons to achieve dients of propellants. [6,9–10] Oxygen balance, enthalpy of formation
long-range attacks and efficient damages. Meanwhile, they are also and density are the key characteristics taken into consideration in the
widely applied in civil fields, such as aerospace, mining, tunneling and development of HEDMs and closely related to their fundamental physic-
demolition, which contributed enormously to the progress and prosper- ochemical properties like detonation velocity, heat of explosion, burn-
ity of mankind. [1–3] Most energetic materials are composed of a molec- ing rate, specific impulse, critical detonation diameter, etc. [11–19] The
ular framework bearing covalently bonded oxidizer moieties called ex- heat of explosion usually increases by the introduction of numerous ex-
plosophoric groups. Superior performance requires an effective balance plosophoric groups, which also leads to a weakening of chemical bonds.
within the composition of the target molecule for intramolecular redox This explains why superior detonation performances are usually accom-
reactions, namely combustion or detonation with the formation of only panied by high sensitivities and low stability. From a practical point
gaseous products, carbon oxides, water and nitrogen. A large amount of of view, acceptable sensitivity and stability are important factors to be
energy and gaseous products are released in a short time during those considered when developing new energetic materials. [20–23]
redox processes, exerting high pressures on its surroundings. [4] During the past decades, exploring new structures with superior en-
According to different application purposes, energetic materials can ergetic performances has been the focus of energetic materials commu-
be classified as explosives, propellants and pyrotechnics, among which, nity. [24] Much efforts have been made to synthesize new HEDMs with
explosives and propellants normally require higher energy-density lev- energetic performances comparable to or superior to the benchmark
els to achieve required detonation or propulsion parameters. [5] In gen- HMX. From a chemical point of view, HEDMs are created by combin-
eral, propellants are combustible substances which undergo deflagration ing molecular frameworks with explosophoric groups. The molecular
resulted by the redox reactions with surface burning mechanism, in con- framework is commonly used as a fuel for reactions with attached ex-
trast, the redox reactions of explosives are far more rapid, resulting in plosophoric groups, releasing high energy. Hence, the energetic perfor-
the physical phenomenon of detonation. [6–7] Both the detonation per- mances of HEDMs can be improved by two main strategies: (i) build-
formances of explosives and propulsion efficiencies of propellants are ing more energetic molecular frameworks, and (ii) introduction of more
determined by their chemical compositions and structures. [7,8,14] In energetic and/or oxygen-rich explosophoric groups. In this brief ac-

∗
Corresponding authors.
E-mail addresses: [email protected] (J. Zhang), [email protected] (B. Wang), [email protected] (A.B. Sheremetev).

https://doi.org/10.1016/j.fpc.2021.09.005
Received 8 July 2021; Received in revised form 25 September 2021; Accepted 26 September 2021
Available online 1 October 2021
2667-1344/© 2022 Xi’an Modern Chemistry Research Institute. Publishing services by Elsevier B.V. on behalf of KeAi Communications Co. Ltd. This is an open
access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/)
J. Zhou, J. Zhang, B. Wang et al. FirePhysChem 2 (2022) 83–139

count, recent successful efforts to synthesize HEDM using promising kJ/mol). The example of pyrrolidine clearly shows that the replacement
building blocks, including a variety of frameworks and explosophoric of CH2 by NH led to increased density compared to cyclopentane (0.866
groups, are described. The first part of the account focuses on build- g/cm3 vc. 0.745 g/cm3 ). It is important to note that the installation of
ing blocks for the design of HEDMs, including both frameworks and ex- explosophoric groups to the azacyclane framework can usually be im-
plosophoric groups. It then outlines the recent successful manipulation plemented more simply.
of these building blocks for the design of HEDMs. New structural design From the data on the properties of strained cyclic and cage hydrocar-
concepts and promising synthetic strategies related to understanding en- bons and their aza-analogs there are several important trends to note.
ergetic performance-structure relationships are discussed. The first is that the density a framework increases with (i) the transi-
tion from monocyclic to polycyclic molecules; (ii) replacement of single
2. Building blocks for the design of HEDMs bonds by double bonds in the ring; (iii) replacement of CH2 units with
NH units. The second trend is that the enthalpy of formation, the higher
The density and enthalpy of formation are additive characteristics the (i) the smaller the cycle size; (ii) more small cycles in the polycyclic
of the chemical compound. This means that the denser and more en- and cage molecule; (iii) more CH2 or CH units are replaced with NH or
ergetic building blocks are used to construct a molecule, the higher N units, respectively.
the final performance. [7,8,25] The contributions of many structural As the majority of energetic compounds are heterocycles, it is not
moieties to both density [19,26] and thermochemical characteristics surprising that heterocyclic frameworks are the most popular choice in
[27,54,117] are known. This makes it possible to compare different moi- the creation of new target products. [32,33,55,56] Structures and basic
eties and to roughly estimate the result that can be expected with a cor- physical properties of various azoles and azines can be found in Table 2
responding substitution in the structure of the molecule. This visual and [56–68].
simple approach is useful for quickly assessing the attractiveness of a From the data in Table 2 several interesting trends for azoles and
hypothetical energetic compound. azines can also be noted. First, the density of heterocycles increases with
At the same time, the major challenge in the engineering of energetic the accumulation of nitrogen atoms in a ring. In this case, the density
compound is the absence of a direct correspondence between the prop- depends not only on the number of heteroatoms, but also on their rel-
erties of a molecule and how exactly the building blocks are combined ative position. Second, heterocycles in which heteroatoms are directly
when it is created. This arises from the complex nature of the interaction bonded to each other have a higher enthalpy of formation than analogs
between the parts of the molecule, depending on the main framework in which heteroatoms are separated by carbon atoms. An increase in the
and the type, number and position of functional groups on it, as well as number of nitrogen atoms in the ring leads to an increase in its enthalpy
on intermolecular interactions that determine the crystal packing. Af- of formation. Third, from a chemical point of view, with an increase in
ter the synthesis of a new target energetic compound, it is very useful the number of nitrogen atoms in a ring, the number of points of diversity
to experimentally determine both its real density and the enthalpy of that serve for the functionalization of this framework decreases.
formation, and use these data to adjust the contributions of structural From a practical standpoint, a synthetic pathway to a framework, or
units. more often its functionalized derivative, suitable for the required modi-
fication, should be simple and concise, reliable, and scalable in order to
2.1. Frameworks of HEDMs provide fast access to large quantities of the target material.
In the following sections, we will highlight some examples of using
Most traditional energetic materials derive their energy from the frameworks to create energetic compounds that have been published in
heat released on the oxidation of their carbon frameworks by the oxygen recent years.
carried by the nitro group. Various molecular structures, including lin-
ear hydrocarbons (alkanes, alkenes, alkynes), carbo or hetero cyclanes 2.2. Explosophoric groups of HEDMs
(from 3- to 8- numbered), [28–29] strained or caged molecules, [30,31]
azoles or their linearly linked assembiles, azines, and fused heterocy- For the first time, the classification of selected functional groups,
cles, [32,33] have been applied as frameworks for energetic materials. called explosophoric groups, which impart explosive properties to a
To create a new high-energy compound, the choice of the ideal molecu- compound, was proposed by Pletz in 1935 [69]. Plets identified eight
lar framework is undoubtedly the first key issue to be solved. While the groups of explosophores and predicted the possibility of modifying
usual aliphatic and aromatic frameworks do not disappear from the field its classification with the addition of newly discovered explosophores.
of view of researchers, strained cyclic and cage hydrocarbons and their Since then, the field of chemistry known as the chemistry of energetic
aza-analogs are attracting increased attention of the explosives commu- compounds has seen remarkable advancement, and now new opportu-
nity. [34–36] Table 1 presents selected examples and provides primary nities are opening up to synthesize previously unavailable products with
characteristics for the hydrocarbons most commonly used in this cate- ever-increasing efficiency. Indeed, Pletz’s pioneering classification was
gory. [37–50] later modified and refined [70–72].
In compact strained molecules, the angles and bond lengths devi- A variety of more complex explosophoric units, usually constructed
ate noticeably from the "normal" values, and the resulting steric stress from several previously known explosophoric groups, have since been
provides the appearance of strain energy. This strain affects an increase reported. High-oxygen carriers, usually based on N-O, N-Hal, Hal-O,
in the negative heat of combustion and an increase in the positive en- and N-N bonds, as well as nitrogen-rich endothermic groups, are key
thalpy of formation in comparison with unstrained analogs (see, Table explosophoric motifs for energetic materials. The explosophoric groups
1). [51–54] However, the remaining challenge is the functionalization and units used recently in the design of energetic compounds are sum-
of the strained molecule in a predictable manner. marized in Table 3. [73–94]
It should be noted that analogs of the aforementioned frameworks, Most of the above groups are bonded to the framework by one bond,
where part of the CH or CH2 units are replaced by N or NH units, re- namely C-C or C-N or C-O, and thus occupy one of the free positions on
spectively, have also been studied. However, most of the parent azacy- it. Azo- and azoxy groups (entries 19 and 20, respectively) require the
clanes are unstable and their properties similar to those presented in formation of two covalent bonds, and are a bridge between two iden-
Table 1 are absent in the literature. Nevertheless, based on the avail- tical or different frameworks. Nitramino (entry 3) and perchlorylamino
able data, it can be noted that such a replacement leads to an increase (entry 14) groups can form either two covalent bonds, or one of them
in both the enthalpy of formation and density. For example, replacing can be replaced by an ionic bond; the acidic proton in these groups fa-
CH2 of cyclopropane with NH led to significantly increased enthalpy of cilitates the synthesis of salt with various bases. The triazene unit (entry
formation for aziridine compared to cyclopropane (92 kJ/mol vc. 11.3 21) has three binding points, forming a complex framework.

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Table 1
Hydrocarbon building blocks of energetic frameworks

With a certain degree of convention, the groups summarized in privileged position in energetic material chemistry. More significantly,
Table 3 can be divided into those, that are responsible for the combus- the nitro group is the most commonly used subunit to create more com-
tion of the carbon backbone using the oxygen/halogen carried by the plex explosophoric units (entries 2-11).
group (entries 1-16), and those that "pump" the target compound with The number of hydrogen atoms that can be oxidized by a group can
an increased positive enthalpy of formation (entries 17-22). be taken as a measure of the oxidative efficiency of that group. With
Indeed, the energy of most traditional energetic compounds comes the Hox index in hand, one can easily compare the oxidative capacity
from the combustion of the carbon backbone, consuming oxygen sup- of different explosophoric groups. As can be seen from the Table 3, the
plied by the nitro groups. Not surprisingly, nitro compounds occupy a leader in excess oxygen content is trinitromethylazoxy group with Hox of

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Table 2
Heterocyclic building blocks of energetic frameworks[56]

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Table 3
The explosophoric groups and units of organic energetic compounds.

References to the group

Entry Group/Unit Sum Formula (M.w.) [Hox ][a] [Mox ][b] usage

1 -NO2 NO2 4 0.087 [73]

(46.01)
2 -ONO2 NO3 6 0.097 [74]
(62.00)
3 =NNO2 N2O2 4 0.067 [75]
(60.01)
4 -C(NO2 )3 CN3O6 8 0.053 [76]
(150.03)
5 -C(NO2 )2 F CN2O4F 5 0.041 [77]
(123.02)
6 -C(NO2 )2 NF2 CN3O4F2 6 0.038 [78]
(156.03)
7 -C(NO2 )2 N3 CN5O4 4 0.027 [79]
(146.04)
8 -C(NO2 )2 NH4 CH4N3O4 0 0 [80]
(122.06)
9 -N(O)=NNO2 N3O3 6 0.067 [81]
(90.02)
10 -N=N(O)C(NO2 )3 CN5O7 10 0.052 [82]
(194.04)
11 -N=N(O)C(NO2 )2 F CN4O5F 7 0.042 [83]
(167.03)
12 -ClO3 ClO3 7 0.084 [84]
(83.45)
13 -OClO3 ClO4 9 0.090 [85]
(99.45)
14 =NClO3 ClNO3 7 0.072 [86]
(97.46)
15 -NF2 NF2 2 0.038 [87]
(52.00)
16 -N=N(O)F N2OF 3 0.037 [88]
(82.01)
17 -N(O)=NOCH3 CH3N2O2 -0.5 -0.007 [89]
(75.05)
18 -N(O)=NCN CN3O -1 -0.014 [90]
(70.03)
19 -N=N- N2 0 0 [91]
(28.01)
20 -N=N(O)- N2O 2 0.045 [92]
(44.01)
21 -N=N-N= N3 0 0 [93]
(42.02)
22 -N3 N3 0 0 [94]
(42.02)
Note: [a] The number of hydrogen atoms that can be oxidized by this group. [b] The number of oxidizable hydrogen atoms per g-mol of the group.

10 (entry 10). It should be noted that Hox characterizes a moiety of any structures formation, etc., can enter unequal contributions to ΔHf 0 .
size that occupies one position at the framework. On the other hand, the Some examples of the nitro group contributions to the enthalpies of for-
Mox index characterizes the mass efficiency of an explosophoric group, mation for various compounds are shown in Table 4. [95–115]
describing the number of oxidizable hydrogen atoms per g-mol of that The inclusion of a bridging atom or group between the nitro group
group. The most effective, and at the same time light, is the nitroxy and the carbon atom of the framework has a very significant effect on
group with Mox of 0.097 (entry 2). the enthalpy of formation. So, for example, if an oxygen bridge is lo-
During intramolecular redox process, weak N-O and N-F bonds are cated between the nitro group and the carbon atom, as is the case in
broken, and new strong C-O and H-F bonds are formed, which is ac- nitro esters, a significant decrease in the enthalpy of formation occurs.
companied by the release of energy. Here it should be noted that in As illustrated in Table 4, when replacing the C-NO2 fragment with C-
cases where the explosophoric group is bonded to the carbon atom of ONO2 one, the energy decreases by ca. 48 kJ/mol (for example, compare
the framework through the C-O bond (as in esters of nitric and perchlo- entries 4 and 7).
ric acids, see entries 2 and 13), the heat effect of the redox reaction is Trinitromethyl moiety (see Table 2, entry 4) and more complex ex-
reduced, since part high-strength C-O bonds are already there before the plosophoric groups, including it as a subunit (see Table 2, entry 10),
start of the reaction. have made a significant impact on research in the field of energy mate-
As to be expected, explosophoric groups, when combined with rials science [5,8]. In addition to a high increase in oxygen balance, the
framework, enter various contributions to the enthalpy of formation trinitromethyl moiety contributes to an increase in the total molecular
(ΔHf 0 ) of the final compound. However, even the same group, de- density, and the proximity of nitro groups causes a positive contribution
pending on the type of the framework, the presence and position of to the enthalpy of formation (see, Table 4, entries 2 and 3). However,
other groups, conjugation, steric hindrances, the possibility of resonance molecules bearing a trinitromethyl moiety usually have insufficient ther-

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Table 4
Varying the сontributions, ΔNO2 , of the nitro group to the enthalpy of formation of various compounds.

(continued on next page)

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Table 4 (continued)

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Table 4 (continued)

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Table 4 (continued)

Note: [a] Enthalpy of formation of gas at standard conditions (experimental value); [b] Enthalpy of formation of liquid at
standard conditions (experimental value); [c] Enthalpy of formation of solid at standard conditions (experimental value).

mal and chemical stability. Typically, for energetic compounds bearing N(NO2 )Me. The replacement of nitramino moiety by isomeric oxy-NNO-
this group, the thermal decomposition temperatures ranged from 110 to azoxy moiety tends to increase enthalpy of formation by 25–63 kJ/mol
150°C [116]. per one N2 O2 moiety [137], and in so doing contributes markedly to
By changing a nitro group of the trinitromethyl moiety by a fluo- the overall energetic performance. Typically, methoxydiazene N-oxides
rine atom, the thermal stability of final compound bearing fluorodini- have higher melting points than isomeric nitramines, but usually have
tromethyl moiety are usually increased by 5-50°C [116], while the melt- slightly lower densities. All alkoxydiazene N-oxides are thermally stable
ing point decreases. In general, fluorodinitromethyl compounds are less and chemically inert.
sensitive to impact and friction than their trinitromethyl cousins. At the Linear bi- and tri-nitrogen units (Table 3, entries 19-21) are excellent
same time, their active oxygen content is significantly reduced (Table 2, bridging groups for the design of energetic azole or azine ensembles. The
entry 4 vs. entry 5). However, replacing NO2 with F brings the main contributions to the enthalpy of formation of various nitrogen bridges
damage to the enthalpy of formation, which decreases by 154-259 kJ in comparison with other bridges are shown in Table 7. [138–149]
per fluorine (Table 5, entries 1-5). [117–119] Using unchanged substituents, namely the model phenyl group, the
It is noteworthy that when a nitro group of the trinitromethyl moiety effect of the composition and length of the bridge on the energetics of
is replaced by a proton and acidic dinitromethyl moiety was neutralized the molecule can be clearly seen.
with ammonia to form the ammonium salt, the observed decrease in In general, there are two main trends in the data in Table 7. First,
enthalpy formation is similar to that of replacing NO2 with F (Table 5, from an energy point of view, nitrogen bridges are the most attractive
entry 6 vs. entries 1-5). [120] and, moreover, do not require oxygen to be converted to a gaseous prod-
It should be noted that the change of a nitro group of the trini- ucts during combustion or explosion. The more nitrogen atoms are in the
tromethyl moiety with a fluoroamino group is practically equivalent, bridge chain, the greater its contribution to the enthalpy of formation.
and only slightly reduces the enthalpy of formation (Table 5, entry 7). Second, the oxidation state of nitrogen atoms in the bridge significantly
While all of the above modifications of trinitromethyl moiety are affects the energy of the bridge. The maximum contribution is made by
accompanied by a decrease in the enthalpy of formation, those that lead the azo bridge (entry 5); both its oxidation, to the N-oxide (see entries
to its growth are also possible. It is well known that 268 kJ mol−1 of 6 and 7), and its reduction, to the hydrazo group (entry 5), leads to a
energy is gained from the conversion of the trinitromethyl moiety to decrease in the enthalpy of formation.
azidodinitromethyl moiety (Table 5, entry 8). The acetylene bridge is similar to the azo bridge in terms of its con-
On the other hand, the possibility of increasing the enthalpy of tribution to the enthalpy of formation (compare entries 3 and 5), but
formation is associated with the introduction of N-N bonds into the for the full realization of the energy stored in it, additional oxygen is re-
molecule. This, in particular, can be achieved if one or more nitrogen quired for oxidation during combustion or explosion. It is not surprising
atoms are located between the nitro group and the carbon atom (Table that various combinations of the endothermic acetylene moiety and ni-
2, entries 3 and 9) [121]. Some examples of the N-nitro group contribu- tro groups have attracted the attention of researchers for several decades
tions to the enthalpies of formation for various compounds are shown [150].
in Table 6. [122–136] Among the actively used explosophoric groups, the azodo group is
Cursory inspection of the data presented in Table 6 demonstrates the leader in terms of a positive contribution to the enthalpy of forma-
that replacing C-NO2 with N-NO2 makes a positive contribution by in- tion of its compounds. The energy gain that is observed when different
creasing the enthalpy of formation. When replacing N-H with N-NO2 , groups are replaced by an azido group are summarized in Table 8. [151–
the result depends on the surrounding molecular architecture, and the 167]
enthalpy of formation can both increase and decrease. As seen in Table 8, when a proton is replaced by the azido group
Considerable attention is paid to the combined explosophoric units, (entries 1-10), the contribution of this substitution to the enthalpy of
including the azoxy group as a subunit (Table 3, entries 9-11 and 16- formation lie in the range from 295 to 372 kJ/mol. The result of re-
18). Because of the inherent greater endothermicity of the N=N bond, placing NO2 with N3 (entries 11-12) is also consistent with the above
the construction of moieties with a longer heteroatom chain on its ba- contribution from the azido group.
sis is very useful for creating energetic compounds with a high en- It should also be pointed out that some heterocycles can also be
thalpy of formation. Unfortunately, data on the experimental enthalpies regarded as explosophore units. For example, unsubstituted furazan
of formation of compounds of this type are very rare in the open [60] and tetrazole [61] are capable of detonating upon initiation; det-
literature. onation velocities are 6170 and 4770 m s−1 , respectively. The par-
For example, the methoxy-NNO-azoxy unit (Table 3, entry 17) have ent 1,2,4,5-tetrazine explodes when trying to isolate it from a solution
the same elemental composition as the N-methyl-N-nitroamine group, R- [62].

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Table 5
Comparison of the enthalpies of formation of compounds with trinitromethyl and X-dinitromethyl groups.

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Table 6
Varying the сontributions, Δ(N)NO2 , of the nitramino group to the enthalpy of formation of various
compounds

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Table 7
Contributions of various bridging groups to the enthalpy of formation of diphenyl compounds and ditetrazoles.

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Table 7 (continued)

2.3. Complementary Functional groups of HEDMs ing to an improvement in technical properties is accompanied by a loss
of energy. A clear change in the basic characteristics of energy com-
It is impossible to introduce nitro- and other explosophoric groups pounds observed with the introduction of additional non-explosophoric
into all possible positions of a framework and expect that the product groups can be found in Table 9. [168–187]
will remain as stable as the original framework. As can be seen from Table 9, additional groups significantly affect all
The presence of additional non-explosophoric groups in the characteristics. Both a decrease and an increase in the melting point can
molecules of energetic compounds is usually due to several reasons. be achieved. Oxygen substituents usually do not significantly reduce the
First, from a practical point of view, the presence of certain struc- oxygen balance; however, they significantly reduce the enthalpy of for-
tural units can (i) increase thermal stability and/or chemical resis- mation. The C-amino group usually increases the density, but decreases
tance; (ii) reduce sensitivity to shock and friction; (iii) impart in- the enthalpy of formation. In contrast, the N-amino group increases the
creased density, (iv) improve compatibility with other components of enthalpy of formation but decreases the density. The properties of iso-
energetic materials; (v) endow the molecule with specific properties mers, with different locations of the amino group in the molecule, differ;
(for example, photosensitivity, etc.). Secondly, this additional group a similar trend is also observed for other substituents. Thus, predictable
can appear in the molecule during synthesis, being an integral part tuning of various important characteristics of energetic compounds may
of the available building blocks from which the target compound is be made by adjusting substituents on the nitrated framework.
synthesized. An important additional group used for the construction of energetic
In any case, these additional groups should be selected such that compounds is the N-oxide moiety [188]. Unlike the above additional
their negative effect on the energy of the molecule would be minimal, groups, its distinctive feature is the presence of active oxygen capable
and the required adjustment of the above technological qualities would of oxidizing carbon and/or hydrogen atoms. Furthermore, the insertion
be the most rational. of an N-oxide moiety into azoles and azines can significantly increase
The most typical non-explosophoric groups installed in the molecules the melting and decomposition temperatures and provide favorable con-
of energetic compounds to correct their useful technical properties are ditions for the formation of a denser packing of molecules into crystals,
methyl, methylene, hydroxyl, ether, carbonyl, amino, imino, fluorine, reducing the enthalpy of formation significantly less than the C-O bond
etc. However, as a rule, the modification of an energetic molecule lead- (Table 10). [189–217]

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Table 8
Contributions of the azido group to the enthalpy of formation of diverse compounds.

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Table 8 (continued)

As shown in Table 10, the effect of the N-oxide moiety on the prop- than 20 reviews have been published covering various aspects of the
erties of the molecule depends on the type of framework, the number chemistry, properties, and applications of energetic compounds [221].
and location of substituents. An overview such as this can only hint at enormous structural diversity.
A dipolar single bond of the N-oxides, N+ -O− , provoking a redistribu- In the next section, we will give selected examples illustrating the use of
tion of the electron density in the molecule, has a significant stabilizing various explosophoric groups in the design of targeted highly energetic
effect for some frameworks. It served as the basis for the development of compounds.
the theory of creating stable high-nitrogen compounds with alternating
charges [218]. As a result, 1,2,3,4-tetrazine-1,3-dioxides were synthe- 3. HEDMs based on different frameworks
sized [219].
On the other hand, it should be pointed out that the N-oxide group In recent decades, by combining different frameworks and ex-
can also increase the reactivity to electrophilic and nucleophilic attack, plosophoric groups, impressive advances have been made in the de-
as well as expand the range of reagents with which the modified com- sign and synthesis of the energetic compounds whose detonation perfor-
pound can react [220]. mances are comparable to or superior to HMX. Most HEDMs are based
Probably, today the number of synthesized examples of various ener- on a variety of heterocyclic rings. Although a wide variety of innova-
getic compounds is approaching 10000. In the last two years alone, more
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Table 9
Some examples of the influence of the introduction of additional groups into energetic compounds on the change in
properties.

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Table 9 (continued)

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Table 9 (continued)

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Table 9 (continued)

[a] Melting point. [b] Oxygen coefficient. For a compound with the molecular formula Cx Hy Fv Nw Oz ,
𝛼 = (z+v/2)/(2x+y/2). A compound with 𝛼 > 1 is an oxidizer. [c] Density at 298 K obtained from X-ray analysis. [d]
Enthalpy of formation at standard conditions (experimental value).

tive energetic compounds have been published in recent years, our focus excellent detonation properties (D = 9310 m/s, P = 40.3 GPa) which are
will be restricted to only the most striking examples of molecular design comparable to those of CL-20.
based on framework structures, ensembles of nitrogen heterocycles, and Although HEDMs with a cage molecular skeleton exhibit excellent
condensed frameworks. It is instructive to consider the approaches that detonation performances, synthetic pathways to most of them are usu-
have been employed to synthesize energetic compounds with various ally quite long and expensive.
structurally novel heterocyclic architectures. In 2018, Chen et al. developed a simple and efficient strategy in
Highly nitrated carbocyclic caged structures, as well as their aza which low-cost caged fuel and oxidizer components are combined into
and aza/oxa analogs, have long attracted researchers as target energetic a molecule through coordination bonds, yielding a densely packed
compounds [222].The ability to vary the properties of caged heterocy- highly symmetric perovskite skeleton, (the so-called molecular per-
cles by manipulating their structures makes such systems highly attrac- ovskite [224] with a general formula of ABX3 , which topologically
tive to energetic material discovery and accounts for the widespread mimic the cubic structure of the very well-known inorganic perovskites
occurrence of their nitrated derivatives. but have at least one organic molecular component (usually the A com-
In 2018, Luo et al. reported an elegant multistep synthesis of ponent), was the simplest high-symmetry structure for ternary com-
2,4,4,6,8,8-hexanitro-2,6-diazaadamantane 7 from available cycloocta- pounds.) ((H2 DABCO) [M(ClO4 )3 ]) (H2 DABCO = C6 H14 N2 )(Fig. 1a).
1,5-diene. [223] The approach that was employed in the synthesis of [225,226] Unlike other HEDMs, this study discovered a new form
compound 7 is summarized in Scheme 1. The unusual caged compound of energetic structures, including caged skeletons, were cyclo-1,3,5,7-
7 exhibited high density (1.959 g/cm3 at 153 K) and positive enthalpy tetramethylenene-2,4,6,8-tetranitramine (HMX) match at combustion
of formation (169.9 kJ/mol), high thermal stability (Td = 235°C) and and detonation performances. In the original paper [225, 227], deto-

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Table 10
Some examples of the influence of the N-oxide moiety into heterocycles on the change in properties.

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Table 10 (continued)

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Table 10 (continued)

[a] Melting point; [b] Oxygen coefficient. For a compound with the molecular formula Cx Hy Fv Nw Oz ,
𝛼 = (z+v/2)/(2x+y/2). A compound with 𝛼 > 1 is an oxidizer; [c] Density at 298 K obtained from X-ray analysis; [d]
Enthalpy of formation at standard conditions (experimental value).

nation performances are calculated differently for salt structures and ifuroxan. Recently, a synthesis of two isomeric dinitrobifuroxans, 11a
the results are shown in Fig. 1b. In this review paper, the detonation and 11b, differing in the position of the N-oxide groups, was disclosed by
properties estimated by DFT calculation of enthalpy of formation are Makhova and co-workers. [232] The one-pot synthetic strategy is highly
carried out with the results shown in Table 11. efficient but the reaction yields need to be further improved. In 2017,
Over the past decades, many research groups have used oxadiazoles the same group demonstrated the synthesis of 3-nitro-4-(4-nitrofurazan-
as building blocks that can impart beneficial physical, chemical and en- 3-yl)furoxan 14a and its isomer 14b, with N-oxide inside, using a similar
ergetic properties to target energetic compounds. Among them, 1,2,5- approach (Scheme 2). [233]
oxadiazoles, called furazans, and their oxides, furoxans, are currently The combination of furazan and furoxan units will also lead to ener-
the focus of much attention [228]. getic compounds with brilliant performances, among which 3,4-bis(3-
Furoxan is a significant energetic framework which has been widely nitrofurazan-4-yl)furoxan (DNTF or BNFF) is one of the most widely
applied in the development of HDEMs and achieved great success. used HDEMs. [234] DNTP is a highly powerful explosive, surpassing
[221c] 4,4’-Dinitro-3,3’-azofuroxan is a unique HDEM with a crystal HMX in detonation performances: at a density of 1.937 g/cm3 , it has
density of 2.02 g/cm3 and the highest experimental detonation velocity a detonation velocity of 9250 m/s. In 2018, Shreeve and co-workers
of 10000 m/s for currently known explosives. [229] According to recent described the synthesis of dinitroterfuroxan 21a using a 1,3-dipolar cy-
calculations, the energy-density levels of HEDMs can be significantly cloaddition reaction followed by oxidation of the amino group to the
improved by replacing the furazan unit with a furoxan one. [230] In- nitro group. [235] Remarkably, the experimental performance of this
deed, replacing one furazan unit with furoxan in 3,4-bis(4-nitrofurazan- compound have been published by Pepekin and Afanas’ev in 2005,
3-yl)furoxan can lead to an increase in density by 0.1 g/cm3 and detona- [236] but the synthesis was not disclosed at that time. In 2019, Wang’s
tion velocity by 700 m/s. [231] A similar trend is observed for dinitrob- group reported the synthesis of 21b and its isomer 21a using the re-

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Scheme 1. Step-by-step synthesis of 2,4,4,6,8,8-hexanitro-2,6-diazaadamantane 7.

Fig. 1. Synthesis of caged energetic perovskites and their energetic properties.

Table 11 GPa) than the isomer with close N-oxides, 21b (𝜌=1.91 g/cm3 , D=9503
Detonation properties of energetic molecular perovskite estimated by DFT cal- m/s, P=41 GPa). Starting from the linear structure 19, the polycyclic
culation of enthalpy of formation. compound 20 was obtained. With a high density of 1.895 g/cm3 , rea-
𝜌[a] (g cm−3 ) Q[b] (kJ g−1 ) D[b] (km s−1 ) P[b] (GPa) OB[c] (%) sonable sensitivities (IS=19 J, FS=80 N), and comparable detonation
performances relative to HMX, compound 20 represents the first exam-
RDX 1.82 5.59 8.634 33.3 −21.6
HMX 1.90 5.57 8.892 36.2 −21.6 ple possessing furoxan fused 1,2-diazocine structure.
DAP-1 2.02 6.39 8.781 36.5 −22.0 The density of energetic materials can be significantly improved
DAP-2 2.04 6.12 8.591 35.2 −21.3 by combining fused frameworks with N-nitroamino groups, where
DAP-4 1.87 5.87 8.806 35.2 −27.9 the N-H moiety tends to form strong hydrogen bonds. In 2015
Note: [a] 𝜌 is the density of the powder sample measured by capillary powder and 2016, Klapötke group reported their synthetic studies towards
X-ray diffraction at room temperature; for classic explosives, 𝜌 is the crystal 1,5-di(nitramino)tetrazole and 1,1’-dinitramino-5,5’-bitetrazole, two N-
density; [b] Q is the heat of detonation, D is the detonation velocity, and P nitroamino based energetic structures with high energy density levels
is the detonation pressure; The detonation parameters were estimated by DFT (𝜌=1.96 g/cm3 , D=9967 m/s, P=43.4 GPa; 𝜌=1.93 g/cm3 , D=10142
calculations and the empirical K-J equation; [c] Oxygen Balance based on CO2 m/s, P=45.6). [238] Despite the outstanding detonation performances,
for Ca Hb Nc Md Cle Of , M as alkali metal ion, were calculated by: OB[%] = 1600[f- their applications are limited due to the high sensitivities. In 2017,
2a-(b-e+d)/2]/MW , where MW is molecular weight. Zhang group achieved their first synthesis of ICM-101, a planar energetic
molecular structure with an extremely high density of 2.037 g/cm3 (at
170K) and good detonation performances (D = 9481 m/s, P = 41.9 GPa).
verse sequence of reactions, performing first an oxidation and then a [239] The combination of good detonation performance and decreased
ring closure reaction (Scheme 3). [237] Importantly, different N-oxide sensitivities makes ICM-101 a promising explosive candidate that war-
orientations in the terfuroxan affect the properties of the isomers. The rants further investigation. All these structures and results exemplify the
isomer, where the N-oxides are located outside, 21a, is denser (𝜌 = 1.98 rational designs of HEDMs via hydrogen bonding effect to balance high
g/cm3 ) and has a higher energetic performances (D = 9867 m/s, P = 45 performance and acceptable molecular stability. (Scheme 4)

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Scheme 2. The synthesis of isomeric dinitrobifuroxans.

Similarly, a series of HEDMs based on N-nitroamino structures were cations 5-nitrotetrazole-2-oxide and 3,3′-dinitro-bi(1,2,4-triazole)-1,1′-
successfully developed by Shreeve group, (Scheme 5) including the dioxide give promising energetic salts, including hydroxylammonium
synthesis of 5,5’-dinitramino-3,3’-azo-1,2,4-oxadiazole (34), [240] 5- salts showed the best detonation performances.
nitramino-3,4-dinitropyrazole (35), [241] N-(2,3,5,6-tetranitro-4H,9H- As a promising explosophoric unit, the tetrazole ring benefits from
dipyrazolo [1,5-a:5′,1′-d] [1,3,5] triazin-4-yl)nitramide (36), [242] 3- high nitrogen content and enthalpy of formation, leading to excellent
nitramino-4-(5-nitramino-1, 2, 4-triazol-3-yl)furazan (37), [243] 3,4- performances. To improve the energetic properties of tetrazoles, in
di(nitramino)furazan (38), [244] 3,6-dinitramino-1,2,4-triazolo [4,3-b] 2012, Klapötke et al. has been synthesized 5,5’-bitetrazole N,N’-dioxide
[1,2,4,5]tetrazine (39), [245] 3,6-nitramino-1,2,4-triazolo [4,3-b] and its dihydroxylammonium salt (TKX-50). (Scheme 7) The formation
[1,2,4,5]tetrazine-7-N-oxide (40), [246] 4,4’-dinitramino- [3,3’- of N-oxide moieties in 5,5’-bistetrazole-1,1’-dioxide was achieved dur-
bi(1,2,5-oxadiazole)]-5,5’-dioxide and 4,4’-diamino- [3,3’-bi(1,2,5- ing the course of tetrazole ring-closure. [257] Intensive research into
oxadiazole)]-2,2’-dioxide (41 and 42). [247] the properties and applications of TKX-50 has been carried out due to
N-Oxide azoles, in the presence of an NH proton in the ring, are iso- its impressive detonation performances (𝜌=1.91 g/cm3 , D=9698 m/s,
merized into usually more thermodynamically stable N-OH tautomers. P=42.4 GPa) and easy accessibility. [258]
The stability and increased density of the N-oxide/N-OH azoles make Fused heterocyclic frameworks have been widely applied in the
this structural motif an important unit in the energetic materials design. design and synthesis of energetic materials [73a,221h,259]. Typically
That the synthesis of N-oxide/N-OH azoles remains a topic of intense coplanar polycyclic structures are characterized by increased density
interest for several decades reflects the enduring relevance of this func- and enthalpy of formation, and they are resistant to high temperatures,
tionality [220c,248] which are ideal for the development of HEDMs. When N-oxide moiety is
Various oxidizing agents are used to oxidize azoles to the correspond- incorporated into a fused heterocyclic framework, the energetic perfor-
ing N-OH derivatives, including trifluoroperacetic acid, [249] potas- mance can be further improved. [260] The most striking example is the
sium peroxomonosulfate (Oxone®), [250] hypofluorous acid, synthetic efforts towards [1,2,3,4]tetrazino [5,6-e] [1,2,3,4]tetrazine
[251] H2 O2 /phtalic anhydride, [252]3-chlorobenzenecarboperoxoic N,N’,N",N"’-tetraoxides (TTTO) isomers. [261] As can be seen in Scheme
acid [253] and hypofluorous acid [254] and etc. For example, the 2, two isomers are possible for TTTO, which differ in the arrangement
commercially available Oxone® has recently been used to synthesize of N-oxides. [262] Early theoretical estimates indicated that TTTO may
5-nitrotetrazole-2-oxide, the derivatives of which have exhibited good have a relative performance of 2.2 times that of HMX, which is likely to
detonation performance. [255] This simple operation also revealed be the performance limit for conventional CHNO energetic structures.
a direct synthetic pathway to novel energetic 1,2,4-triazole N-oxides [263] The synthesis of TTTO was considered unrealistic for a long period
(Scheme 6). [256] N-OH azoles are acids and can be converted to of time. However, in 2016, Churakov et al disclosed the first success-
salts; using nitrogen-rich energetic cations, they form energetic salts of ful synthesis of TTTO and its properties. [264] The employed synthetic
independent interest. For example, in combination with nitrogen-rich routes for the preparation of TTTO are shown in Scheme 8. The synthetic

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Scheme 3. The synthesis of terfuroxan.

strategy was based on the stepwise closure of two 1,2,4,5-tetrazine N,N’- back in 2014, Shreeve group had reported their regioselective oxidation
dioxide rings through the generation of oxodiazonium ions and their in- strategies towards the synthesis of N-oxide and 2,4-di-N-oxide deriva-
tramolecular coupling with tert-butyl-NNO-azoxy groups. [265] TTTO tives of highly dense 1,2,4,5-tetrazine structures. The two electron-rich
has acceptable thermal stability; however, its low resistance to hydrol- substituents only and the combination of both electron-deficient and
ysis can complicate its practical use. electron-rich substituents will lead to the formation of mono- and di- N-
To create the fused 1,2,3,4-tetrazine 1,3-dioxide, the key precursor oxide products, respectively. [270] (Scheme 11) It is noteworthy that no
is a (het)aromatic amine with a tert-butyl-NNO-azoxy group in the o- examples of azido tetrazine oxidations had been achieved and only one
position, which is first converted to N-nitroamines. The tetrazine ring- example of oxidation of a tetrazolo-tetrazine had been reported before
closure is the result of the reaction between the tert-butyl-NNO-azoxy Chavez group’s work. The addition of two equivalents of hypofluorous
group and the intermediate oxodiazonium ion generated from the ni- acid led to exclusive production of 3,6-diazido-1,2,4,5-tetrazine oxide.
troamino group, with the loss of the tert-butyl cation during treatment Similarly, mono- and di- N-oxide product could be formed through the
with reagents such as N2 O5 , NO2 BF4 , P4 O10 , PCl5 , SO3 , AcCl/AlCl3 , addition of one and two equivalent of hypofluorous acid. The use of ex-
Ac2 O/H2 SO4 , etc. [219, 266] (Scheme 9) cess hypofluorous acid did not produce any additional oxidation of the
Recently, Churakov et al. reported the preparation of a bicyclic com- substrates. The detonation performance properties of 76 and 80 were
pound 65, which is a combination of tetrazine dioxide and triazole oxide proved to be high-performing HEDMs, with theoretical detonation ve-
units, by treating aminotriazole 66 with an HNO3 /H2 SO4 /Ac2 O mix- locities of 9.6 and 10.03 km/s, and theoretical detonation pressure of
ture. Compound 65 has a melting point of 141°C, followed by an onset 45.78 GPa and 41.3 GPa, respectively. (Scheme 12)
of decomposition at 194°C, indicating a good thermal stability. Com- It is known that the presence of hydrogen bonds in nitrogen-
pound 65 is an acid and readily gives the K-salt (Scheme 10). [267] rich fused nitroheterocycles contributes to an increase in the den-
N-Oxides of isomeric 1,2,4,5-tetrazine can also be synthesized. How- sity of HEDMs, which improves the energetic performance. [271] In
ever, in this case, the existing tetrazine ring is oxidized by various 2015, Chavez et al modified the synthesis of the fused heterocyclic
reagents. structure, 4-amino-3,7,8-trinitropyrazolo- [5,1-c] [1,2,4]triazine (PTX)
Another highly oxidized nitrogen-rich aromatic heterocycles was (Scheme 13). [272] PTX exhibited HMX-like explosive performances
achieved by Chavez group in 2017. [268] Unlike Churakov group’s at an X-ray crystal density of 1.946 g/cm3 , while its thermal stabil-
sequential closure strategy for the construction of N-oxide moieties, ity, sensitivity to impact, friction and spark showed large safety mar-
Chavez group chose an impressive azido/amino group directed late- gins. These properties are the result of the formation of hydrogen
stage oxidations for the synthesis of azido/tetrazolo 1,2,4,5-tetrazine bonds.
N-oxides. [269] The oxidation of 1,2,4,5-tetrazines is difficult due to Clearly, the constructions of different energetic building blocks can
the strong electron deficient properties of the N-rich backbones. Further efficiently improve both the energetic properties and detonation per-

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Scheme 4. The preparations of compound 28 and ICM-101.

formances of HEDMs. Some strategies, including the introductions of have attracted considerable attentions. [273] From synthetic perspec-
maximized N-oxides and abundant hydrogen bondings in nitrogen- tive, the nitrolysis of ethyl ester and acetonyl groups, nitrosation and
rich heterocycles, the constructions of compact cage molecular skele- oxidation of secondary nitroalkanes, as well as the oxidative nitration of
tons, were widely applied and achieved great success. However, the oximes and chloroximes (by N2 O4 and N2 O5 respectively), are the most
building blocks as molecular skeletons normally need great synthetic widely applied methods for the synthesis of dinitromethyl moiety and
efforts. its salts, from which, trinitromethyl moiety can also be formed through
further nitration. [275] In 2016, the synthesis of 3,5-bis(dinitromethyl)-
4. HEDMs with oxygen-rich explosophoric groups 1,2,4-triazole and its energetic mono- and dianionic salts was re-
ported by Shreeve et al. [274] (Scheme 14a) Monohydrazinium 3,5-
A typical energetic compound consists of a framework, which acts bis(dinitromethyl)-1,2,4-triazolate 85 exhibited great detonation prop-
as a “fuel” unit, and covalently bonded oxidizer units, among which the erties of high density (1.94 g/cm3 ), acceptable sensitivities (22 J, >360
most popular are nitro, nitramino and nitroxy groups. Most interest is N), good detonation velocity (9271 m/s), and good pressure (41.0 GPa).
focused on high-density organic CHNOF compounds that contain the el- In 2018, Fan et al synthesized of 5,5’-bis(trinitromethyl)-3,3’-bi-1H-
ements in the ratio required for combustion to gaseous products in the 1,2,4-triazole 90 and its salts. As shown in Scheme 14b, a mixture of
absence of air. As indicated in section 2.2 of this review, replacing the oxamidrazone 87 with ethyl-3-ethoxy-3-iminopropionate hydrochloride
nitro group with groups carrying more oxidizing elements (-C(NO2 )3 , was cyclized in acetic acid and lead to the formation of 5,5’-bis(acetic
-C(NO2 )2 NF2 and others) increases the energy performance due to im- acid ethyl ester)-3,3’-bi-1H-1,2,4-triazole 88 by neutralizing the above-
proved oxygen balance and density. mentioned mixture. Further alkalization, acidification and nitration will
During the past decade, azoles bearing C- and N-attached dini- give the desired compound 90. The treatment of 90 with 50% aque-
tromethyl and trinitromethyl groups and their energetic salts as HEDMs ous hydroxylamine resulted in the formation of Hydroxylammonium

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Scheme 5. Synthetic efforts towards HEDMs with N-nitroamino structures.

Scheme 6. Synthetic pathway to selected N-OH azoles and their salts.

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Table 12
Properties of the selected energetic compounds from the considered in Section 3.

Fw OB<CO2> [ c ] , d[ d ] , ΔHf [ e ] , Tdec [ f ] , P[ g ] , D[ h ] ,

Compound Formula [g/mol] IS[ a ] , [J] FS[ b ] , [N] [%] [g/cm3 ] [kJ/mol] [°C] [GPa] [m/s]

C8 H8 N8 O12 408.19 - - -31.35 1.959 -169.9 235 40.3 9310

(153 K)

C4 N6 O8 260.08 3.9 26 0 1.97 (298 -448.9 146 41.2 9525

K)

C4 N6 O7 244.08 2.6 67 -6.56 1.920 -417.5 146 38.8 9180

(298 K)

C4 N6 O7 244.08 2.8 82 -6.56 1.934 -417.5 140 39.4 9230

(298 K)

C4 N8 O6 280.11 19 80 -34.27 1.895(298 -894.9 161.6 39.6 9417

K)

C6 N8 O10 344 3 35 -9.3 1.98 (298 -667.8 130.7 45 9867

K)

C6 N8 O10 344 3 40 -9.3 1.91 (298 -579.2 146.5 40.8 9503

K)

C2 H2 N12 O4 258.11 <1 <5 -6.2 1.93 (298 -932 107 45.6 10142
K)

C2 H2 N8 O4 202.09 1 <5 -7.91 1.93 (298 -486 110 43.4 9967

K)

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Table 12 (continued)

Compound Formula Fw IS[ a ] , [J] FS[ b ] , [N] OB<CO2> [ c ] , d[ d ] , ΔHf [ e ] , Tdec [ f ] , P[ g ] , D[ h ] ,

[g/mol] [%] [g/cm3 ] [kJ/mol] [°C] [GPa] [m/s]

C4 H2 N8 O6 258.11 5 60 -18.59 1.99 (298 -166 210 41.9 9481

K)

C4 H2 N10 O6 286.12 2 10 -16.77 1.902 -487.2 140 37.5 9190

(298 K)

C3 H2 N6 O6 218.08 4 40 -7.33 1.97 (298 -173.8 135 41.6 9430

K)

C7 H3 N11 O10 401.16 3 20 -21.93 1.937 -521 117 38.8 9226

(298 K)

C4 H3 N9 O5 257.12 18 250 -28 1.92 (298 -548 128 39 9258

K)

C2 H2 N6 O5 190.07 <1 <5 0 1.899 -287 99 40.5 9376

(298 K)

C3 H2 N10 O4 242.11 3 >5 -19.82 1.91 (298 -740 138 38.3 9301
K)

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Table 12 (continued)

Compound Formula Fw IS[ a ] , [J] FS[ b ] , [N] OB<CO2> [ c ] , d[ d ] , ΔHf [ e ] , Tdec [ f ] , P[ g ] , D[ h ] ,

[g/mol] [%] [g/cm3 ] [kJ/mol] [°C] [GPa] [m/s]

C3 H2 N10 O5 258.11 1 5 -12.39 1.93 (298 -593 114 41.0 9503

K)

C4 H2 N8 O8 290.1 3 20 -5.51 1.91 (298 -461.6 74 40.8 9381

K)

C4 H2 N8 O8 290.10 2 20 -5.51 1.94 (298 -430.8 91 41.7 9472

K)

CHN5 O3 131.07 - - 6.1 1.94 (173 -308.6 ∼120 40.4 9447

K)

CH4 N6 O4 164.11 4 60 0 1.85 (173 -218.7 157 39.0 9499

K)

C4 H8 N10 O8 324.2 >40 >360 -19.74 1.90 (298 -213 217 39.0 9087
K)

C4 H2 N8 O6 258.1 10 360 -18.59 1.92 (298 -290 191 36.2 8729

K)

C2 H8 N10 O4 236.15 20 120 -27.1 1.877 -446.6 221 42.4 9698

(298 K)

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Table 12 (continued)

Compound Formula Fw IS[ a ] , [J] FS[ b ] , [N] OB<CO2> [ c ] , d[ d ] , ΔHf [ e ] , Tdec [ f ] , P[ g ] , D[ h ] ,

[g/mol] [%] [g/cm3 ] [kJ/mol] [°C] [GPa] [m/s]

C2 N8 O4 200.07 - - 0 2.0-2.3 -966 - 60 10900

C2 N10 O 196.09 1.5 10 -16.32 1.904 -967 130 45.8 10030

(293 K) (onset)

C2 H2 N8 O2 170.09 6 109 -28.22 1.932 -576 150 41.3 9600

(293 K) (onset)

C5 H2 N8 O6 270.12 - 324-360 0 1.946 -3702 288 36.04 8998

(300 K)

Note:
a
IS: impact sensitivity
b
FS: friction sensitivity
c
OB<CO2> : oxygen balance, W=(xO-2yC-1/2zH)1600/M
d
d: density
e
ΔHf : enthalpy of formation
f
Tdec. : thermal decomposition temperature
g
P: detonation pressure
h
D: detonation velocity.

Scheme 7. One pot synthesis of TKX-50 from dichlororglyoxime.

salt 91, which exhibited a high density of 1.97 g/cm3 and an excellent sity, oxygen-rich fused polynitromethyl derivative 101 and 102 were
calculated detonation velocity and pressure of 9468 m/s and 44.9 GPa created employing the reaction of 5,6-dichlorofurazano [3,4-b]pyrazine
[276]. Similar protocol was used for preparation of 5-trinitromethyl- with 5-(trinitromethyl)- and 5-(1-fluoro-1,1-dinitromethyl)tetrazoles,
1,2,4-oxadiazoles. [277] respectively [279]. Polynitromethyl moieties of target products 101
Recently, Sheremetev et al, upon fluorination of 3-(dinitromethyl)- and 102 are suppled in the cascade process nucleophilic substitution -
1,2,4-triazol-5-yl)furazans, synthesized the corresponding fluorodini- ring opening - nitrogen release - ring closure, where C-(trinitromethyl)-
tromethyl derivatives 95 and 96. The pathway from the available pre- and C-(fluorodinitromethyl)tetrazoles are key building blocks
cursor to the target product 95 is shown in Scheme 15 [278a]. Azocom- (Scheme 16)
pound 96 has been prepared using a similar protocol [278b]. High den-

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Scheme 8. First synthesis of TTTO.

Scheme 9. Possible mechanism for the formation of the tetrazine dioxide structure.

Scheme 10. Synthesis of 1-hydroxy-1H-[1,2,3]triazolo[4,5-e][1,2,3,4]tetrazine 5,7-dioxide 65.

Scheme 11. Synthesis of mono- and di-N-oxides of 1,2,4,5-tetrazines

In 2018, Ge et al reported their synthesize and thermal research on In 2017, Yang et al reported the synthesis of furazan bear-
the dihydroxylammonium salt of bis(dinitromethyl)-furazan. [280] The ing nitramino and dinitromethyl groups and its energetic salts.
compound 108 exhibited a high crystal density of 1.938 g/cm3 (at 296 [281] (Scheme 18) Among the salts obtained, the dihydroxylammonium
K) and detonation properties (D = 9679 m/s, P = 41.5 GPa), as well as salt structure (DNMNAF) showed excellent comprehensive properties
moderate impact sensitivities (14 J), which achieved a high level of bal- (𝜌=1.930 g/cm3 at 293 K, Td = 175 °C, P = 43.0 GPa, D = 9646 m/s,
ance between high energetic density and low sensitivity. (Scheme 17) IS = 8 J, FS = 64 N, OB=5.3%) as promising high-performance HEDM.

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Scheme 12. Synthesis of 6-aminotetrazolo[1,5-b][1,2,4,5]tetrazine 3,7-dioxide (80).

Scheme 13. Modified synthesis of PTX.

Scheme 14. Synthesis of C-attached di- and trinitromethyl 1,2,4-triazoles

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Scheme 15. Structures and synthesis of fluorodinitromethyl derivatives (95 and 96).

Scheme 16. Synthesis of polynitromethyl moieties of target products (101 and 102) from salts of 5-(trinitromethyl)tetrazole or 5-(fluorodinitromethyl)tetrazole.

Scheme 17. Synthesis of bis(dinitromethyl)-furazan salts from 3,4-dicyanofurazan.

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Scheme 18. Synthesis of 3-dinitromethyl-4-nitraminofurazan (DNMNAF).

Scheme 19. Synthesis of furoxans bearing fluorodinitromethyl groups.

In 2020, Wang et al reported the synthesis of two novel the highest crystal density of 2.00 g/cm3 among fluorodinitromethyl-
high-energy regioisomers, which are a combination of fluoro- functionalized CHNOF compounds reported thus far as well as excel-
dinitromethyl groups with isomeric terfuroxan frameworks, 3,4- lent detonation performances (D=9509 m/s, P=42.6 GPa), which were
bis(3-fluorodinitromethylfuroxan-4-yl)furoxan (BFTF-1) and 3,4-bis(4– comparable to CL-20 and also significantly higher than those of BFTF-2
fluorodinitromethylfuroxan-3-yl) furoxan (BFTF-2). [282] Both isomers (𝜌=1.91 g/cm3 , D=9196 m/s, P=38.8 GPa). The striking difference in
were derived from a common precursor, 4-(chlorohydroxyminomethyl)- the density of above isomers (see Table 13) indicated that regiochemi-
3-cyanofuroxan (112) (Scheme 19). For the synthesis of BFTF-1, at the cal modulation will play an important role in the design and synthesis
first step, a terfuroxan framework was created, which provides the posi- of energetic materials.
tion of the oxygen atoms of the N-oxides on the terminal furoxan rings Whereas the first publications in the open literature on the syn-
outside, synthesizing compound 118. Then, step by step, the nitrile thesis of N-(X-dinitromethyl) functionalized azoles appeared about
groups of compound 118 were transformed into fluorodinitromethyl 30 years ago [283], recently this type of compounds have become
groups. On the contrary, for the synthesis of BFTF-2, the fluorodini- widespread as energetic materials. Typically, N-dinitromethyl and
tromethyl group should be installed into the monocyclic furoxan first, N-trinitromethyl groups are formed by the nitration of N-acetonyl
obtaining compound 115, and only then the isomeric terfuroxan frame- moiety; the mechanism of this reaction has been studied in de-
work should be built, where the oxygen atoms of the N-oxides on the tail [284]. Various derivatives of azoles were used in this reaction
terminal furoxan rings are located inside the molecule. BFTF-1 exhibited [285].

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Table 13
Properties of the selected energetic compounds from the considered in Section 4.

OB<CO2> [ c ] , d[ d ] , ΔHf [ e ] , Tdec [ f ] , P[ g ] , D[ h ] ,

Compound Formula Fw [g/mol] IS[ a ] FS[ b ] , [N] [%] [g/cm3 ] [kJ/mol] [°C] [GPa] [m/s]

C4 H7 N9 O8 309.15 22 J >360 -18.11 1.94 -173.1 235 41.0 9271

(298 K)

C6 H8 N14 O14 500.03 5J 144 -6.4 1.97 -44.9 191 39.9 9468
(298 K)

C5 HFN8 O7 304.11 13%[ i ] - -15.78 1.884 -82.8 167 - -

(296 K)

C8 N14 O13 500.17 11 J 130 -9.59 1.892 -704 128 35 9010

(298 K) (onset)

C8 F2 N12 O9 446.16 14 J 190 -21.51 1.901 -376 157 33 8590

(298 K) (onset)

C4 H8 N8 O11 344.15 14 J 280 -4.65 1.938 -27.7 156.9 41.54 9679

(298 K)

(continued on next page)

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Table 13 (continued)

Compound Formula Fw [g/mol] IS[ a ] FS[ b ] , [N] OB<CO2> [ c ] , d[ d ] , ΔHf [ e ] , Tdec [ f ] , P[ g ] , D[ h ] ,

[%] [g/cm3 ] [kJ/mol] [°C] [GPa] [m/s]

C3 H8 N8 O9 300.14 8J 64 -5.3 1.930 -62.1 175 43.0 9646

(293 K)

C8 F2 N10 O14 498.14 5 70 -3.2 2.00 390.1 116 42.6 9509

(296 K) (onset)

C8 F2 N10 O14 498.14 6.5 110 -3.2 1.91 383.9 136 38.8 9196
(296 K) (onset)

C6 F2 N12 O12 470.13 9J 240 3.40 1.926 -64.62 217 31.54 8613
(293 K)

C8 H2 N10 O 434.15 4J 120 -3.68 1.954 -391.12 166 39.7 9394

(293 K)

C8 N14 O20 312.17 9J 215 10.50 2.02 -522 125 40.0 9320
(293 K)

(continued on next page)

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Table 13 (continued)

Compound Formula Fw [g/mol] IS[ a ] FS[ b ] , [N] OB<CO2> [ c ] , d[ d ] , ΔHf [ e ] , Tdec [ f ] , P[ g ] , D[ h ] ,

[%] [g/cm3 ] [kJ/mol] [°C] [GPa] [m/s]

C6 N12 O16 496.13 7J 40 93.52 1.997 -580 160 37.8 9182

(298 K)

C6 N10 O13 420.12 14 J - 3.8 1.94 -365.5 135 38.0 9200

(298 K) (onset)

C2 HN7 O6 219.07 5 80 11.0 1.97 -311.4 109.3 38.5 9.22

(298 K)

C8 F2 N10 O14 344.11 - - 6.72 2.02 -500 233 44.9 9735

(298 K)

C8 H4 N12 O20 588.18 36% - 5.4 1.88 -350.4 169.5 32.8 8360
(298 K) (onset)

418.14 5.6 J 104 -3.6 1.963 -322 174 40.6 8800

C6 H4 F2 N8 O12 (293 K) (onset)

(continued on next page)

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Table 13 (continued)

Compound Formula Fw [g/mol] IS[ a ] FS[ b ] , [N] OB<CO2> [ c ] , d[ d ] , ΔHf [ e ] , Tdec [ f ] , P[ g ] , D[ h ] ,

[%] [g/cm3 ] [kJ/mol] [°C] [GPa] [m/s]

386.14 5.4 J 104 -12.46 1.89 -303 204 33.2 8400

C6 H4 F2 N8 O10 (293 K) (onset)

537.19 15 295 -13.4 1.933 -1100 230 25.5 7850

C9 H6 F3 N9 O15 (298 K) (onset)

668.23 16 240 -4.78 1.94 -719.7 203 38.9 9156

C10 H4 N16 O20 (298 K)

C7 H8 N14 O10 448.23 2.3 87 -28.55 1.927 -702 206 40.5 9120
(298 K)

C8 H10 N16 O8 458.27 2.9 88 -45.38 1.854 -1010 179 39.2 9170
(298 K)

229.53 - - 3.48 1.88 -388 - 39.40 9180

C2 H4 ClN5 O6 (pycnometric
density)

(continued on next page)

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Table 13 (continued)

Compound Formula Fw [g/mol] IS[ a ] FS[ b ] , [N] OB<CO2> [ c ] , d[ d ] , ΔHf [ e ] , Tdec [ f ] , P[ g ] , D[ h ] ,

[%] [g/cm3 ] [kJ/mol] [°C] [GPa] [m/s]

296.58 - - -21.58 1.87 -712 - 39.31 9125

C4 H5 ClN8 O6 (pycnometric
density)

Note:
a
IS: impact sensitivity
b
FS: friction sensitivity
c
OB<CO2> : oxygen balance; for a compound with the molecular formula of CxHyNwOz, OB<CO2> = 1600 [(z-2x-y/2)/MW], MW – molecular weight
d
d: density
e
ΔHf : enthalpy of formation
f
Tdec. : thermal decomposition temperature
g
P: detonation pressure
h
D: detonation velocity
i
IS: Impact sensitivity shown as frequency of explosions at the impact with energy 4.9 J. (K-44-II impact machine, set no. 1).

Scheme 20. Bitriazoles bearing trinitromethyl, fluorodinitromethyl and difluoroaminodinitromethyl groups

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Scheme 21. Trinitromethyl derivatives of liner and fused dipyrazoles.

The binding of polynitromethyl groups to the nitrogen atom of the compounds offers 141 not only of fundamental interest, but also for po-
azole ring provides such compounds with a higher positive enthalpy of tential practical applications, for example, as promising candidates to
formation than that of their C-linked analogs [286]. new environmentally benign rocket propellants. (Scheme 22)
In 2017, Semenov et al have disclosed the conversion of 2,2’- In 2009, Semenov et al accomplished the synthesis of a diver-
diacetonyl-5,5’-dinitro-bi(1,2,4-triazole) 123 and its 1,2,3-analog 131 sity of N-(X-dinitromethyl)-5-R-tetrazoles [294]. The low stability of
to 2,2’-bis(dinitromethyl) compounds 124 and 132, respectively. This these compounds has been effectively used for their introduction
is followed by nitration, or fluorination, or difluoroamination to into various reactions, where they act as polynitro-nitrilimine equiv-
obtain target products containing trinitromethyl- (125 and 128), alents (Scheme 23a). Later, Pang et al investigated the possibil-
fluorodinitromethyl- (126 and 129) and difluoroaminodinitromethyl ity of using certain salts of N-(dinitromethyl)-5-nitrotetrazole. [295]
(127 and 130) groups (Scheme 20) [287]. In the same year, Zhang et al (Scheme 23b)
independently reported a similar synthesis of fluorodinitromethyl com- In 2010, Semenov et al also described promising methods for the
pound 126, as well as a number of energetic salts from acidic bi(1,2,4- functionalization of N-dinitromethyl azoles, which open up wide pos-
triazole) 124. [288] sibilities for the synthesis of interesting energetic compounds [296].
An analysis of the properties of analogs bearing the –C(NO2 )3 , – Scheme 24 demonstrates some transformations using a tetrazole deriva-
C(NO2 )2 F and –C(NO2 )2 NF2 groups at the nitrogen atom of a hete- tive as an example. It should be noted that compounds 150 and 151
rocycle is very informative for identifying structure-property relation- have a high density (1.92 and 2.06 g/cm3 , respectively).
ships. This has been used in a number of recent papers (see, for example Fluorodinitromethyl-azoxy and polynitromethyl-azoxy are effec-
[289, 290]). In 2018, Sheremetev et al reported two-step method to in- tive explosophoric groups created by Luk’yanov group, which have
stall the N-trinitromethyl moiety to both pyrazole rings of the 4,4’,5,5’- been proved to be able to significantly improve the oxygen bal-
tetranitrobipyrazole (Scheme 21a), an insensitive and thermally sta- ance and energetic performances. [297] Nitromethylazoxy compound
ble framework with high energy-density level. [291] The resulting chemistry has been extensively reviewed by Zlotin and Luk’yanov
new oxidizer, 4,4’,5,5’-tetranitro-2,2’-bis(trinitromethyl)-2H,2’H-3,3’- in 1993 [298], the topic has been reviewed subsequently by Zhang
bipyrazole 135, contains ten nitro groups, which gives it not only a posi- et al in 2016, from an energetic materials chemistry perspective
tive oxygen balance, but also the highest measured X-ray density (2.021 [299]. Several of the more important works are noted here. Scheme
g/cm3 ) for energetic oxidizers composed of carbon, nitrogen, and oxy- 25 provides a clear description of the protocol used to synthesize
gen atoms. The remarkable high density level and high power of this polynitromethyl-azoxy compounds. It should be noted that the steps
novel oxidizer clearly demonstrates that the use of trinitromethyl units used are easy to carry out and do not require expensive reagents.
will significantly improve the energy density level of nitrogen-rich ener- Following this scheme, Luk’yanov group synthesized trinitromethyl-
getic heterocycles. While framework compound 135 constructed from and fluoronitromethyl-ONN-azoxy azoxyfurazans, 159 and FDNAF, re-
two linearly linked pyrazole rings, Kommu et al recently reported the spectively. Then Wang group studies in more detail the preparation
production of a novel green high-density energetic oxidizer from fused and properties of 3,3′-bis (fluoronitromethyl-ONN-azoxy) azoxyfurazan
pyrazolopyrazole using a similar protocol (Scheme 21b). [292] The syn- (FDNAF) [300], which has a high density (𝜌 = 2.02 g/cm3 ) and good
thesized octanitro product 138 also had a high density (1.997 g/cm3 ). stability. A similar protocol was used to synthesize compound 162,
The creation of energetic compounds that are a combination of the N- where the central azoxy group was replaced by the furoxan ring
(polynitromethyl)pyrazole moiety with other heterocycles, for example, (Scheme 26) [301].
with the furazan ring [293], is now widely used. In 2021, Sheremetev Polynitromethyl-ONN-azoxy group is chemically resistant. Scheme
et al reported the preparation of novel (pyrazole-3-yl)furazan frame- 27 demonstrates some useful reactions in which a compound can be
work bearing nitro group in furazan, from which, 3-(3,4-dinitro-1- involved without disrupting this group [302].
(trinitromethyl)-1H-pyrazol-5-yl)-4-nitrofurazan (141) were achieved. The installation of O-attached trinitroethyl and fluorodinitroethyl
The combination of positive enthalpy of formation, high density, favor- groups is of considerable interest for the design of energetic compounds.
able physical and thermal properties, and reasonable sensitivity with It was reported that nucleophilic substitution of the activated leaving
the promising theoretical energetic performance of these oxygen-rich group at the azine ring with trinitroethanol and fluorodinitroethanol

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Scheme 22. The synthesis of 3-(3,4-dinitro-1-(trinitromethyl)-1H-pyrazol-5-yl) -4-nitrofurazan (141).

Scheme 23. Synthesis and reactivity of N-(X-dinitromethyl)-tetrazoles.

Scheme 24. Selected modifications of N-dinitromethyl azoles.

leads to the formation of the corresponding trinitroethoxy and fluoro- plosophoric group of nitramine results in an impressive density level (>
dinitroethoxy derivatives (Scheme 28). The success of these reactions 2.0 g/cm3 ) and detonation properties (D∼9400 m/s, P∼ 42 GPa). In or-
depends on the base used to generate the O-nucleophile [303]. der to synthesize compounds with an energy potential close to that for
The N-attached trinitroethyl group is the time-tested building block CL-20, but less sensitive to mechanical stimuli, in 2017, Luk’yanov et al
for creating energetic compounds. Traditionally, compounds of this type reported the results of a study of the replacement of one or more nitro
are prepared by the Mannich reaction. In 2017, Yang et al reported groups in CL-20 with a trinitroethyl moiety (Scheme 30). [305] The det-
bis-N,N’-trinitroethylation of 3,6-(3-aminofurazan-4-yl)-1,4-dioxa-2,5- onation velocities calculated independently by Smirnov and Khakimov
diazine (180) with trinitriethanol followed by N,N’-dinitration gave tar- according to their procedures were 9050 and 9160 m/s for compound
get product 182 with high density of 1.95 g/cm3 (Scheme 29). [304] 191 and 8800 and 8910 m/s for compound 189, respectively, which are
Over the past decades, CL-20 has been regarded as one of the most comparable to those of HMX.
promising powerful energetic substances. Hunders of studies on the op- High endothermicity is a key factor in the design of HDEMs
timal conditions for the CL-20 synthesis and investigations on its fun- for the new generation of rocket technologies. Taking this into ac-
damental physicochemical properties have been reported. The com- count, in 2020, Luk’yanov et al developed novel caged HDEMs
bination of cage skeleton of hexaazaisowurtzitane and traditional ex- through the incorporation of a high-enthalpy N-azidomethyl moi-

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Scheme 25. Synthesis of 3,3′-bis(polynitromethyl-ONN-azoxy) azoxyfurazan.

Scheme 26. Synthesis of bis(fluorodinitromethyl-ONN-azoxyfurazanyl)furoxan.

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Scheme 27. Reactivity of compounds bearing polynitromethyl-ONN-azoxy groups

Scheme 28. Synthesis of trinitroethoxy and fluorodinitroethoxy azines.

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Scheme 29. Synthesis and nitration of Mannich base from trinitroethanol and 3-amino-4-R-furazan.

Scheme 30. Synthesis of CL-20 analogs bearing trinitroethyl or azidomethyl groups.

ety into the polynitro hexaazaisowurtzitane backbone (Scheme 30). are 2-2.5 times that of CL-20. The complex of attractive properties
among which, two energetic structures of 4-azidomethyl-2,6,8,10,12- makes these compounds promising energetic components for propellant
pentanitrohexaazaisowurtzitane and 4,10-bis(azidomethyl)-2,6,8,12- compositions.
tetranitrohexaazaisowurtzitane exhibited good thermal stabilities (de- Energetic materials containing fluorodinitroethyl moieties exhibit
composition onset 180-205 °C) and high density (1.85-1.93 g/cm3 ). higher energy-density level than the similar nitro-substituted structures
[306] The detonation performances of them exceed those of HMX, and better thermally stabilities and insensitivities than their trinitroethyl
with detonation velocities, pressures and heat values of 9120 and 9170 analogs. Therefore, incorporations of the fluorodinitroethyl groups into
m/s, 40.5 and 39.2 GPa, 6289 and 6126 kJ/kg, respectively. Their a compact framework is expected to provide promising HEDMs with
enthalpies of formation on a unit of mass (up to 2210 kJ/kg) are high performances. In 2019, Luk’yanov et al developed a method for
the highest among the known hexaazaisowurtzitane derivatives and the synthesis of previously unknown CL-20 analogs bearing fluorodini-

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Scheme 31. Synthesis of N-fluorodinitroethyl analogs of CL-20.

Scheme 32. Synthesis of N-(2-fluoro-2,2,-dinitroethyl)azoles

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Scheme 33. Synthesis of perchlorylamino furazan and its energetic salts.

troethyl moieties (Scheme 31) and studied their properties. [307] The acterized. [309] (Scheme 33) Despite the outstanding explosive output
density of 193 is 1.947 g/cm3 , which is significantly higher than that of of perchlorylaminofurazan salts, (𝜌: 1.84∼1.88 g/cm3 , D: 9027∼9180
HMX (1.902 g / cm3), while that of 195 is 1.806 g/cm3 , i.e. it is close m/s, P: 37.81∼39.4 GPa) their sensitivities are relatively high upon im-
to HMX. The thermal stability of 195 is close to that of HMX while the pact, friction or heating.
thermal stability of 193 bearing only fluorodinitroethyl group, is close
to that of CL-20. It has been shown that the replacement of the N-nitro 5. Conclusion and perspective
group in CL-20 with a N-dinitrofluoroethyl group practically does not
change the parameters of mechanical sensitivity and thermal stability, The pursuit of more powerful compounds has always been the eter-
while the introduction of a N-trinitroethyl group reduces them. nal goal of the energetic materials science. Over the past decade, enor-
Recently, the first simple two-step protocol to efficiently pre- mous number of publications related to the design and synthesis of
pare unprecedented N-(2-fluoro-2,2,-dinitroethyl) derivatives of im- new HEDMs reveal that this research field is still full of opportuni-
idazoles, pyrazoles, triazoles, and tetrazoles have been disclosed ties and of great interest to the chemical and material scientists around
[308]. Michael addition of NH-azoles to 1,1-dinitroethene, generated the world. This review attempts to highlight key structural units such
from 1,1,1-trinitroethane, followed by fluorination provides the N- as explosophoric groups and high-nitrogen frameworks for the design
dinitrofluoroethylated nitrogen heterocycles in moderate to good over- of high energy density materials (HEDMs). Recent efforts to create
all yields (Scheme 32). HEDMs with detonation performances comparable to or superior to
In 2020, Sheremetev et al developed the first perchlorylamino HMX are reviewed. A number of modern strategies are highlighted,
heterocycles, perchlorylaminofurazans, through the reaction of N- including: (i) creating more energetic frameworks; (ii) the introduc-
lithiated and N-silylated aminofurazans with FClO3 or Cl2 O7 . Energetic tion of oxygen-rich explosophoric groups to improve the oxygen bal-
salts comprising nitrogen-rich 1,2,4-triazol-based cations and 3-nitro- ance; (iii) construction of dense energy structures by introducing frag-
4-(perchlorylamino)furazan anion whose predicted explosive perfor- ments capable of strong intra- and intermolecular interactions. The bet-
mance was close or superior to that of HMX were synthesized and char- ter understanding of the structure-performance relationship of ener-

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getic compounds will be a great favor to the design of new HEDMs. [19] A.A. Kotomin, M.A. Ilyushin, S.A. Dushenok, Methods for Calculation Of Charac-
From a synthetic point of view, future directions of research will ob- teristics Of Energetic Substances Of Various Chemical Structure, LAP LAMBERT
Academic Publishing, 2020 ISBN: 978-6202682398.
viously focus on more energetic and, at the same time, more sta- [20] D. Badgujar, Review on promising insensitive energetic materials, Cent, Eur. J.
ble target structures that can be easily and quickly synthesized from Energ. Mater. 14 (2017) 821–843, doi:10.22211/cejem/68905.
cheap raw materials. We believe the strategies described in this review [21] C.Y. Zhang, On the energy & safety contradiction of energetic materials and the
strategy for developing low-sensitive high-energetic materials, Chin. J. Energ.
will continue to be effective tools for developing next-generation of Mater. 26 (2018) 2–10, doi:10.11943/j.issn.1006-9941.2018.01.001.
HEDMs. [22] C.Y. Zhang, Origins of the energy and safety of energetic materials and of
the energy & safety contradiction, Propell. Explos. Pyrot. 43 (2018) 855–856,
doi:10.1002/prep.201880931.
Declaration of Competing Interest
[23] S. Zeman, J. Marcela, Sensitivity and performance of energetic materials, Propell.
Explos. Pyrot. 41 (2016) 426–451, doi:10.1002/prep.201500351.
There are no conflicts to declare. [24] (a) J.J Tian, Q.H. Zhang, J.S. Li, Recent advances in energetic molecule synthesis,
Chin. J. Energ. Mater. 24 (2016) 1–9, doi:10.11943/j.issn.1006-9941.2016.01.001;
(b) S.G. Zlotin, I.L. Dalinger, N.N. Makhova, V.A. Tartakovsky, Nitro compounds
Acknowledgments as the core structures of promising energetic materials and versatile reagents for
organic synthesis, Russ. Chem. Rev. 89 (2020) 1–54, doi:10.1070/RCR4908; (c)
This work was supported by the National Natural Science Foundation S.G. Zlotin, A.M. Churakov, M.P. Egorov, L.L. Fershtat, M.S. Klenov, I.V. Kuchurov,
N.N. Makhova, G.A. Smirnov, Y.V. Tomilov, V.A. Tartakovsky, Advanced ener-
of China (grant no. 21805223). A.B.S. is grateful for financial support getic materials: novel strategies and versatile applications, Mendeleev Commun
provided by the Russian Science Foundation (grant no. 20-13-00289). 31 (2021) 731–749, doi:10.1016/j.mencom.2021.11.001.
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