Crystal Growth & Design,
Journal Year:
2023,
Volume and Issue:
23(11), P. 8333 - 8341
Published: Oct. 9, 2023
Co-crystallization
of
the
push–pull
nitriles
NCNR2
(R2
=
Me2
1,
C4H8
2,
C5H10
3,
and
C4H8O
4)
with
iodo-substituted
perfluorobenzenes
(1,4-diiodotetrafluorobenzene
−
1,4-FIB
1,3,5-triiodotrifluorobenzene
1,3,5-FIB)
gave
cocrystals
1·1,3,5-FIB,
2·1,3,5-FIB,
3·1/2(1,4-FIB),
4·1/2(1,4-FIB),
4·2(1,3,5-FIB),
which
were
studied
by
single-crystal
X-ray
diffractometry
(XRD).
The
structure-directing
I···sp-Nnitrile
halogen
bond
(HaB)
in
all
was
identified
based
on
consideration
XRD
geometrical
(bond
length
angles)
parameters
also
Hirshfeld
surface
analysis,
whereupon
observed
HaBs
analyzed
theoretically.
HaB-accepting
role
push–pulling
dialkylcyanamides
conventional
NCR
(R
Alk)
examined
compared
detail
using,
as
model
examples,
structures
3·1/2(1,4-FIB)
(this
work)
AdCN·1/2(1,4-FIB)
(CSD
refcode:
KIHROL).
These
two
cocrystals,
display
similar
supramolecular
organization,
several
quantum
chemistry
methods
including
molecular
electrostatic
potential
natural
orbital
theory
atoms
molecules
combined
NCIPlot
approach,
Kitaura–Morokuma
energy
decomposition
approach.
While
AdCN
is
a
slightly
poorer
sp-N
electron
donor
than
nitrile
exhibit
interaction
energies.
Although
covalent
types
often
strikingly
different
reactivity
patterns,
σ-hole-based
noncovalent
provided
leveling
effect,
resulting
significant
similarities
between
HaB
situations
for
both
species.
International Journal of Molecular Sciences,
Journal Year:
2024,
Volume and Issue:
25(9), P. 4587 - 4587
Published: April 23, 2024
This
study
reveals
a
new
non-covalent
interaction
called
π-hole
halogen
bond,
which
is
directional
and
potentially
non-linear
compared
to
its
sister
analog
(σ-hole
bond).
A
shown
here
be
observed
on
the
surface
of
in
halogenated
molecules,
can
tempered
display
aptness
form
bond
with
series
electron
density-rich
sites
(Lewis
bases)
hosted
individually
by
32
other
partner
molecules.
The
[MP2/aug-cc-pVTZ]
level
characteristics
bonds
33
binary
complexes
obtained
from
charge
density
approaches
(quantum
theory
intramolecular
atoms,
molecular
electrostatic
potential,
independent
gradient
model
(IGM-δginter)),
intermolecular
geometries
energies,
second-order
hyperconjugative
transfer
analyses
are
discussed,
similar
interactions.
That
molecules
substantiated
experimentally
reported
crystals
documented
Cambridge
Crystal
Structure
Database.
importance
design
growth
chemical
systems
synthetic
chemistry,
crystallography,
crystal
engineering
yet
fully
explicated.
Nano Letters,
Journal Year:
2025,
Volume and Issue:
25(2), P. 905 - 913
Published: Jan. 7, 2025
Pnictogen
bond
(PnB)
occurring
on
the
group-15
elements
is
recognized
as
σ-
or
π-hole-based
interaction
that
has
garnered
attention
in
fields
of
anion
recognition
and
organocatalysis.
Due
to
polyvalent
feature
pnictogens
high
directionality,
PnB
possesses
potential
design
convergent
coassembled
materials
with
acceptors
containing
lone
pair
electrons
anions,
which
however
rarely
explored
so
far.
Herein,
we
unveil
role
antimony
(Sb)-based
donors
producing
self-assembled
chiroptical
electron
acceptors.
Steric
effect
electronic
properties
determined
exposure
strength
σ-holes
direct
complexation
between
components.
leads
profound
property
self-assembly
behavior
evolutions
compared
pristine
assembly,
including
crystallinity,
photophysical,
morphological,
properties.
The
complexes
exhibited
an
accelerated
photoisomerization.
Ascribed
multiple
Sb
donors,
amorphous
structures
were
generated,
enabling
formation
glassy
materials.
ChemistrySelect,
Journal Year:
2025,
Volume and Issue:
10(5)
Published: Feb. 1, 2025
Abstract
The
fourth
period
metal
fluorides
acting
as
a
Lewis
acid
form
binary
compounds
with
nitrogen‐containing
bases
(HCN,
NHCH
2
,
and
NH
3
),
which
the
calculations
are
carried
out
at
MP2
ab
initio
level
AVTZ
AVQZ
basis
set
employed
by
CBS
method.
AIM
IGMH
analyses
further
indicate
that
metal‐N‐bases
(M─N)
bonding
exists
in
complexes.
strength
of
interactions
is
ranging
from
−4.76
to
−56.54
kcal/mol.
M─N
exhibits
partially
covalent
nature
characterized
negative
energy
density
large
interaction
energy.
With
decrease
electronegativity
substituents
on
base,
energies
increase.
dominated
electrostatic
all
complexes,
whereas
induction
dispersion
cannot
be
ignored
either.
Molecules,
Journal Year:
2023,
Volume and Issue:
28(7), P. 3133 - 3133
Published: March 31, 2023
The
experimental
structural
features
of
chalcogen
bonding
(ChB)
interactions
in
over
34,000
linear
fragments
R-Ch⋯A
(Ch
=
S,
Se,
Te;
R
C,
N,
O,
A
Te,
F,
Cl,
Br,
I)
were
analyzed.
bond
distances
dR-Ch
and
the
interaction
dCh⋯A
investigated,
functions
δR-Ch
δCh⋯A
introduced
to
compare
data
involving
different
Ch
atoms.
calculated
by
normalizing
differences
between
relevant
ChB
with
respect
sum
covalent
(rcovR
+
rcovCh)
van
der
Waals
(vdW)
radii
(rvdWCh
rvdWA),
respectively.
systematic
comparison
is
presented,
highlighting
role
involved,
atoms
covalently
bonded
Ch,
species
playing
acceptor.
Based
on
results
obtained,
an
innovative
approach
proposed
for
evaluation
categorization
strength
based
data.
ACS Omega,
Journal Year:
2023,
Volume and Issue:
8(36), P. 32828 - 32837
Published: Aug. 30, 2023
For
the
first
time,
sigma
(σ)-
and
lone-pair
(lp)-hole
site-based
interactions
of
SF4
SeF4
molecules
in
seesaw
geometry
with
NH3
FH
Lewis
bases
were
herein
comparatively
investigated.
The
obtained
findings
from
electrostatic
potential
analysis
outlined
emergence
sundry
holes
on
molecular
entity
molecules,
dubbed
σ-
lp-holes.
energetic
viewpoint
announced
splendid
negative
binding
energy
values
for
σ-hole
succeeded
by
lp-hole
analogues,
which
found
to
be
-9.21
-0.50
kcal/mol,
respectively,
SeF4···NH3
complex
as
a
case
study.
Conspicuously,
proper
concurrence
between
strength
chalcogen
chalcogen's
atomic
size
was
obtained,
whereas
reverse
pattern
proclaimed
counterparts.
Further,
higher
preference
YF4···NH3
complexes
elevated
promulgated
over
YF4···FH
ones,
indicating
eminent
role
basicity.
indications
quantum
theory
atoms
generally
asserted
closed-shell
nature
all
considered
interactions.
observation
symmetry-adapted
perturbation
revealed
substantial
contributing
forces
beyond
occurrence
In
comparison,
dispersion
specified
govern
Such
emerging
would
gate
fruitful
forthcoming
applications
bonding
crystal
engineering
biological
systems.
