Combined X-ray Crystallographic and Periodic DFT Study of Supramolecular Organization and Intermolecular Interactions in Crystalline Peroxosolvates of (Nitropyrazolyl)furazans
Crystal Growth & Design,
Год журнала:
2025,
Номер
25(5), С. 1394 - 1405
Опубликована: Фев. 24, 2025
Hydrogen
peroxide
is
a
source
of
active
oxygen,
which
can
optimize
the
negative
oxygen
balance
energy
compounds
and
improve
their
detonation
properties
due
to
formation
crystalline
peroxosolvates.
This
approach
has
been
recently
proposed
but
remains
unexplored
because
number
hydrogen
adducts
energetic
very
limited.
Due
its
acidic
nature,
usually
forms
stable
peroxosolvates
with
basic
or
amphoteric
coformers.
Herein,
compounds,
(nitropyrazolyl)furazanes
C6H5N5O3·H2O2
(1·H2O2),
C6H4N6O5·H2O2
(2·H2O2),
5(C5H2N6O5)·H2O2
(3·1/5H2O2),
were
obtained,
crystal
structures
determined.
Crystal
packings
1–3
are
based
on
same
supramolecular
synthon
formed
by
molecule
three
adjacent
In
this
unit,
H2O2
bonds:
one
furazan
ring
as
proton
donor
two
pyrazolyl
fragments
both
acceptor.
Analysis
metric
parameters
H-bonds
in
previously
published
isostructural
hydrates
1·H2O
2·H2O
indicates
predominant
nature
Periodic
density
functional
theory
(DFT)
calculations
reveal
that
total
sum
bonds
up
10
kJ
mol–1
higher
than
bond
acceptor,
reflecting
H2O2.
The
contribution
molecules
lattice
resulting
about
40–45%.
1·H2O2
exhibits
improved
estimated
comparison
unsolvated
1,
whose
structure
was
also
Язык: Английский
A review of ultra-high temperature heat-resistant energetic materials
Defence Technology,
Год журнала:
2023,
Номер
38, С. 33 - 57
Опубликована: Сен. 19, 2023
Heat-resistant
energetic
materials
refer
to
a
type
of
that
possess
high
melting
point,
stability
and
operational
safety.
By
studying
the
structures
these
has
showed
thermal
can
be
enhanced
by
introducing
amino
groups
form
intra/inter-molecular
hydrogen
bonds,
constructing
conjugate
systems
designing
symmetrical
structures.
This
article
aims
review
physical
chemical
properties
ultra-high
temperature
heat-resistant
compounds
provide
valuable
theoretical
insights
for
preparation
materials.
We
also
analyze
selected
20
with
decomposition
temperatures
higher
than
350
°C,
serving
as
templates
synthesis
various
high-performance
Язык: Английский
Current Advances in Synthesis of Pyrazole Derivatives: An Approach Toward Energetic Materials
Journal of Heterocyclic Chemistry,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 2, 2024
ABSTRACT
Pyrazole
derivatives
are
strategic
structural
motifs
due
to
their
proven
utility
in
preparing
chemicals
biological,
pharmaceutical,
photophysical,
technological,
and
industrial
fields;
therefore,
syntheses
of
pyrazole‐containing
compounds
highly
desirable.
Some
nitrogen‐rich
pyrazoles,
specifically
nitrated
posing
high
density
moderate
thermal
stability,
have
been
used
as
energetic
since
a
amount
energy
is
stored
structures
that
can
be
released
quickly
with
detonation
power
under
external
stimuli
(i.e.,
thermal,
impact,
friction).
These
good
capacity
sensitivity
explosives,
propellants,
pyrotechnics
applications
eco‐friendly
ways.
Therefore,
this
contribution
focuses
on
recent
illustrative
examples
regarding
the
(i)
synthesis
reactivity
especially
works
last
decade,
highlighting
(ii)
analyze
scope.
Язык: Английский
Integration of 1,2,3-Triazine N-Oxide and 2,4,6-Trinitroaniline Moieties for the Design of Heat-Resistant Energetic Compounds
Organic Letters,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 7, 2025
Heat-resistant
energetic
compounds
are
of
great
importance
in
the
field
material
chemistry.
Here,
we
report
a
practical
synthesis
series
fused-ring
via
combination
1,2,3-triazine
N-oxide
and
2,4,6-trinitroaniline
moieties.
Starting
from
known
compound
4,6-diamino-2-chloropyrimidine-5-carbonitrile
(1),
nucleophilic
substitution
followed
by
one-step
nitration
introduced
three
nitro
groups
onto
benzene
ring
moiety,
simultaneously.
The
resulting
4-7
exhibited
high
decomposition
temperature
(Td
>
250
°C)
as
well
relatively
good
detonation
properties
low
sensitivities.
Язык: Английский
Combination of 1,2,4-Oxadiazolone and Pyrazole for the Generation of Energetic Materials with Relatively High Detonation Performance and Good Thermal Stability
Crystal Growth & Design,
Год журнала:
2024,
Номер
24(13), С. 5706 - 5711
Опубликована: Июнь 24, 2024
Oxadiazoles
are
the
satisfactory
structural
units
of
energetic
materials
due
to
high
densities.
However,
practical
use
most
oxadiazole
compounds
in
is
limited
by
their
low
thermal
decomposition
temperature
(<180
°C).
In
this
work,
3-(3-nitro-1H-pyrazol-4-yl)-1,2,4-oxadiazol-5(4H)-one
(6)
with
relatively
detonation
performance
(Dv
=
8315
m
s–1;
P
29.22
GPa)
and
good
stability
(Td
275.9
°C)
has
been
successfully
synthesized
introduction
a
pyrazole
backbone
into
skeleton,
which
better
than
HNS
7612
m·s
–1;
24.3
GPa).
addition,
compound
6
was
using
green,
low-toxicity
three-step
process
(cyclization,
amination,
hydrolysis)
rather
highly
toxic
cyanogen
bromide.
To
investigate
correlation
between
structure
6,
calculations
Hirshfeld
surface
analysis,
2D-fingerprint
plots,
electrostatic
potentials
were
performed.
This
provides
guide
synthesizing
stability.
Язык: Английский
The skeleton of 5,7-fused bicyclic imidazole-diazepine for heat-resistant energetic materials
Defence Technology,
Год журнала:
2022,
Номер
27, С. 193 - 199
Опубликована: Сен. 16, 2022
In
light
of
the
low
yields
and
complex
reaction
routes
some
well-known
5,5-fused
5,6-fused
bicyclic
compounds,
a
series
5,7-fused
imidazole-diazepine
compounds
were
developed
with
high
by
only
two
efficient
steps.
Significantly,
seven-membered
heterocyclic
ring
has
stable
energetic
skeleton
multiple
modifiable
sites.
However,
rarely
reported
in
area
materials.
Three
neutral
1,
2
4
synthesized
this
work.
To
improve
detonation
performances
corresponding
perchlorate
1a
2a
further
developed.
The
physicochemical
all
newly
experimentally
determined.
All
prepared
exhibit
decomposition
temperatures
(Td:
243.8–336
°C)
mechanical
sensitivities
(IS:
>15
J,
FS:
>280
N).
Among
them,
velocities
(Dv
=
7651
m/s)
7600
are
comparable
to
that
typical
heat-resistant
material
HNS
7612
m/s).
Meanwhile,
temperature
(Td
336
°C;
IS
32
J;
FS
>
353
N)
superior
318
5
250
Hence,
thermostability,
adjustable
performance
have
clear
tendency
open
up
new
space
for
development
Язык: Английский
A heat-resistant and insensitive energetic material based on fused triazolo-triazine
Journal of Molecular Structure,
Год журнала:
2024,
Номер
1325, С. 141052 - 141052
Опубликована: Дек. 9, 2024
Язык: Английский
A Facile Method for Assessing the Change in Detonation Properties during Chemical Functionalization: The Case of NH2→NHNO2 and NH2→=N+=N− Conversions
The 17th International Electronic Conference on Synthetic Organic Chemistry,
Год журнала:
2022,
Номер
60, С. 48 - 48
Опубликована: Ноя. 14, 2022
A
simple
and
fast
procedure
for
estimation
of
the
effect
chemical
functionalization
on
change
in
detonation
properties
energetic
materials
is
reported.
The
consists
two
levels.
Computations
at
Level
1
can
be
performed
with
a
pocket
calculator.
At
2,
quantum-chemical
calculations
are
needed,
but
these
include
only
three
computational
tasks:
vacuum-isolated
molecule
relaxation
(PBE/DND)
→
crystal
structure
prediction
(COMPASSII)
cell
(PBE/DND).
Thus,
we
have
analyzed
transformation
both
aromatic
aliphatic
amines
into
corresponding
nitramines
diazo
compounds.
indicated
that
density
(dc)
solid-state
enthalpy
formation
(ΔHf)
always
positive
increase
properties,
while
2
revealed
most
sensitive
to
such
transformation.
Язык: Английский