Decrypting the Unusual Structure and σ-Hole Interactions of the XC(NO2)3 (X=F, Cl, Br, and I) Compounds Using Quasi-Atomic Orbitals
Molecules,
Journal Year:
2025,
Volume and Issue:
30(9), P. 1986 - 1986
Published: April 29, 2025
This
work
reports
the
quasi-atomic
orbital
analysis
of
XC(NO2)3
(X=F,
Cl,
Br,
and
I)
compounds
shows
that
interactions
between
C-N
σ
bonds
lone
electron
pairs
on
halogen
atom
oxygen
atoms
nitro
groups
may
contribute
to
unusually
short
C-X
distances
observed.
While
presence
a
σ-hole
compound
not
be
obvious
from
density
distribution,
an
intermolecular
forces
NH3--XC(NO2)3
complexes
suggests
-hole
interaction
nitrogen
pair
X
(X=Cl,
in
linear
N--X-C
configuration,
where
electrostatics
exchange
dominate.
The
bond
these
systems
is
shown
have
noticeable
covalent
character,
which
captured
polarization
energy
term.
Complexation
with
ammonia
nucleophile
affect
electronic
structure
entire
compounds,
notably
oxygen/halogen
bonds.
Language: Английский
Integrated experimental and computational investigations of crystal structure, and photophysical properties of 2,7-dibromo-9-(4-halobenzylidene)-9H-fluorene frameworks
Journal of Molecular Structure,
Journal Year:
2025,
Volume and Issue:
unknown, P. 142171 - 142171
Published: March 1, 2025
Language: Английский
Halogen Bonds Formed by Halogen’s p/π-Hole in Molecules Help Shape Crystalline Materials
Crystal Growth & Design,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 24, 2025
Language: Английский
Supramolecular assembly governed by tetrel, CN⋅⋅⋅π and other weak noncovalent interactions in two acrylonitrile derivatives with D-π-A topology: crystallography, optical properties and theoretical studies
Journal of Molecular Structure,
Journal Year:
2024,
Volume and Issue:
1320, P. 139650 - 139650
Published: Aug. 17, 2024
Language: Английский
Synthesis and Structure of Unsymmetrical Anthracenyl-Isoxazole Antitumor Agents Via the Diastereoselective Bromination of 3-(9′-Anthryl)-Isoxazole Esters
Crystals,
Journal Year:
2024,
Volume and Issue:
14(3), P. 256 - 256
Published: March 5, 2024
In
pursuit
of
unsymmetrical
precursors
for
the
novel
series
anthracenyl-isoxazole
amide
(AIM)
antitumor
agents,
a
substituted
anthracenes
were
subjected
to
bromination
and
re-aromatization
in
our
study,
during
which
we
solved
four
single
crystal
X-ray
diffractometry
(Sc-xrd)
structures
report
herein.
The
C-9
nitrile
oxide,
after
its
reaction
with
bromine,
was
isolated,
but
when
re-aromatization,
it
returned
starting
10-bromo
oxide
1,
did
provide
an
accurate
structure,
R
=
0.018.
10-halogenated
3-(9’-anthryl)-isoxazole
esters
re-aromatization.
Surprisingly,
yields
obtained
presence
isoxazole
reasonably
good
(62–68%
isolated
yields),
major
diastereomers
allowed
characterization
using
Sc-xrd.
penta
bromo
product
2
showed
trans,
cis
relationship
bromines
on
A-ring
anthracene,
observed
that
unit
cell,
atropisomers
displayed
1:1
ratio
at
chiral
axis
between
anthrancene
rings.
Similarly,
10-chloro
3
indicated
structure.
A
base-induced
afforded
3,10-dihalogenated
analogues
selectively
very
(X
Cl,
89%;
X
Br
92%),
dibromo
4
characterized
improved
unique
diastereomeric
products
suggested
consideration
electrophilic
aromatic
substitution
mechanism
driven
by
stereo-electronic
environment,
imposed
ester
substituent.
promise
application
this
chemistry
future
development
AIM
agents
is
suggested.
Language: Английский
Unveiling the Intermolecular Interactions between Drug 5-Fluorouracil and Watson–Crick/Hoogsteen Base Pairs: A Computational Analysis
ACS Omega,
Journal Year:
2024,
Volume and Issue:
9(23), P. 24831 - 24844
Published: May 31, 2024
The
adsorption
of
5-fluorouracil
(5FU)
on
Watson–Crick
(WC)
base
pairs
and
Hoogsteen
(HT)
has
been
studied
using
the
dispersion-corrected
density
functional
theory
(DFT).
adsorption,
binding
energy,
thermochemistry
for
drug
5FU
WC
HT
were
determined.
most
stable
geometries
near
planar
geometry,
a
higher
preference
than
pairs.
energies
nucleobase
are
consistently
pristine
pairs,
indicating
that
pair
cleavage
is
less
likely
during
drug.
enthalpy
change
formation
5FU–DNA
5FU–nucleobases
enthalpy-driven.
Egap
AT
higher,
suggesting
their
chemical
reactivity
toward
further
reaction
would
be
GC
electron
difference
(EDD)
analysis
shows
significant
decrease
in
aromatic
regions
purine
bases
(adenine/guanine)
compared
to
pyrimidine
bases.
MESP
diagram
5FU–nucleobase
complexes
directional
interaction,
with
positive
molecule
interacting
negative
region
other
molecules.
atoms
show
ρ(r)
values
C═O···H–N
those
N···H/N–H···O.
N···H
intermolecular
bonds
between
pair/drug
nucleobases
weak,
closed
shell
interactions
electrostatic
nature.
noncovalent
interaction
several
new
spikes
engendered
along
an
increase
strength,
which
indicates
H-bonding
stronger
play
dominant
role
stabilizing
complexes.
Energy
decomposition
drug–nucleobase
complex
marginal
contributions
Language: Английский
A comparison of structure, bonding and non-covalent interactions of aryl halide and diarylhalonium halogen-bond donors
Beilstein Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
20, P. 1428 - 1435
Published: June 27, 2024
Halogen
bonding
permeates
many
areas
of
chemistry.
A
wide
range
halogen-bond
donors
including
neutral,
cationic,
monovalent,
and
hypervalent
have
been
developed
studied.
In
this
work
we
used
density
functional
theory
(DFT),
natural
bond
orbital
(NBO)
theory,
quantum
atoms
in
molecules
(QTAIM)
to
analyze
aryl
that
are
monovalent
each
series
include
the
halogens
Cl,
Br,
I,
At.
Within
diverse
set
donors,
found
trends
relate
halogen
length
with
van
der
Waals
radii
non-covalent
or
partial
covalency
bond.
We
also
a
model
calculate
Δ
G
formation
by
linear
combination
%
p-orbital
character
on
energy
σ-hole
donor.
Language: Английский
Data and Molecular Fingerprint-Driven Machine Learning Approaches to Halogen Bonding
Journal of Chemical Information and Modeling,
Journal Year:
2024,
Volume and Issue:
64(21), P. 8201 - 8214
Published: Oct. 29, 2024
The
ability
to
predict
the
strength
of
halogen
bonds
and
properties
bond
(XB)
donors
has
significant
utility
for
medicinal
chemistry
materials
science.
XBs
are
typically
calculated
through
expensive
ab
initio
methods.
Thus,
development
tools
techniques
fast,
accurate,
efficient
property
predictions
become
increasingly
more
important.
Herein,
we
employ
three
machine
learning
models
classify
XB
complexes
by
their
principal
atom
as
well
values
maximum
point
on
electrostatic
potential
surface
(VS,max)
interaction
a
molecular
fingerprint
data-based
analysis.
analysis
produces
root-mean-square
error
ca.
7.5
5.5
kcal
mol–1
while
predicting
VS,max
halobenzene
haloethynylbenzene
systems,
respectively.
However,
prediction
binding
energy
between
ammonia
acceptor
is
shown
be
within
1
density
functional
theory
(DFT)-calculated
energy.
More
accurate
can
made
from
precalculated
DFT
data
when
compared
Language: Английский