Chemistry - A European Journal,
Journal Year:
2023,
Volume and Issue:
29(51)
Published: June 26, 2023
We
report
a
joint
experimental
and
theoretical
study
on
the
stability
reactivity
of
Bin+
(n=5-33)
clusters.
The
alternating
odd-even
effect
reaction
rates
clusters
with
NO
is
observed,
Bi7+
finds
most
inertness.
First-principles
calculation
results
reveal
that
lowest
energy
structures
Bi6-9+
exhibit
quasi-spherical
geometry
pertaining
to
jellium
shell
model;
however,
(n≥10)
adopt
assembly
structures.
prominent
associated
its
highly
symmetric
structure
superatomic
states
magic
number
34e
closed
shell.
For
first
time,
we
demonstrate
unique
s-p
nonhybrid
feature
in
bismuth
rationalizes
within
model,
by
filling
6s
electrons
into
orbitals
(forming
"s-band").
Interestingly,
18e
"s-band"
coincides
compact
for
at
n≤9
but
n≥10,
showing
an
accommodation
s
geometric
structure.
atomic
p-orbitals
also
allow
form
higher
levels,
contributing
preferable
tridentate
binding
units.
illustrate
nature
accommodates
Acta Crystallographica Section C Structural Chemistry,
Journal Year:
2023,
Volume and Issue:
79(6), P. 204 - 216
Published: May 15, 2023
We
report
here
on
the
status
of
research
halogen
bonds
and
other
σ-hole
interactions
involving
p
-block
elements
in
Lewis
acidic
roles,
such
as
chalcogen
bonds,
pnictogen
tetrel
bonds.
A
brief
overview
available
literature
this
area
is
provided
via
a
survey
many
review
articles
that
address
field.
Our
focus
has
been
to
collect
together
most
published
since
2013
provide
an
easy
entry
into
extensive
area.
snapshot
current
by
introduction
virtual
special
issue
compiled
journal,
comprising
11
entitled
`
Halogen,
chalcogen,
bonds:
structural
chemistry
beyond
.'
Crystal Growth & Design,
Journal Year:
2024,
Volume and Issue:
24(13), P. 5494 - 5525
Published: June 24, 2024
This
Article
revisits
the
"Definition
of
Halogen
Bond
(IUPAC
Recommendations
2013)"
[Desiraju,
G.
R.
Pure
Appl.
Chem.
2013,
85
(8),
1711–1713],
recommendations
that
fail
to
include
fundamental,
underlying
concept
(electrophilic)
σ-
and
p-/π-hole
theory
orbital-based
charge
transfer
interactions
accompany
halogen
bond
formation.
An
electrophilic
σ-hole,
or
p-/π-hole,
is
an
electron-density-deficient
region
positive
polarity
(and
potential)
on
electrostatic
surface
side
along,
orthogonal
to,
a
covalently
bonded
in
molecular
entity
leads
development
noncovalent
interaction─a
bond─when
close
proximity
electron-density-rich
nucleophilic
same
another
identical
different
entity,
with
which
it
interacts.
re-examines
characteristic
features
lists
wide
variety
donors
acceptors
participate
bonding.
We
add
caveats
are
essential
for
identifying
bonding
chemical
systems,
necessary
appropriate
use
terminologies
involved.
Illustrative
examples
systems
feature
inter-
intramolecular
bonds
other
crystalline
phase
given,
together
case
study
some
dimer
using
first-principles
calculations.
also
point
out
π-hole/belt
(or
p-hole/belt)
may
develop
derivative
halogenated
molecules
be
prone
forming
when
nucleophiles
similar
entity.
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.
Molecular Physics,
Journal Year:
2024,
Volume and Issue:
unknown
Published: May 24, 2024
Phosphorus-centered
pnictogen
bonds,
similar
to
well-studied
halogen
play
a
vital
role
in
molecular
recognition
and
assembly.
This
study
aims
explain
how
bonds
interact
with
other
noncovalent
interactions.
A
model
system,
phosphines
(PH3),
which
is
also
present
phosphorus
cycles
reduces
planetary
atmospheres,
examined.
The
investigation
of
the
trifluoride
(PF3)
molecule
explores
its
substituent
effects.
To
generate
broad
spectrum
configurations,
specially
tailored
protocol
for
sampling
optimisation
was
implemented.
configurations
were
refined
uncover
primary
interaction
patterns,
clustering
algorithm
revealed
unique
patterns.
report
presents
energy
stability
distribution
all
clusters.
Our
findings
verify
prevalent
presence
identified
by
their
geometric
characteristics
co-occurrence
hydrogen
show
an
almost
linear
correlation.
Another
significant
discovery
correlation
between
various
decomposition
elements,
especially
regarding
electrostatic
overall
binding
energy.
These
results
are
anticipated
significantly
contribute
towards
our
comprehension
non-covalent
interactions
among
phosphorus-containing
molecules
formulation
empirical
models
having
physical
interpretations.
International Journal of Molecular Sciences,
Journal Year:
2023,
Volume and Issue:
24(13), P. 10554 - 10554
Published: June 23, 2023
The
structural
stability
of
the
extensively
studied
organic–inorganic
hybrid
methylammonium
tetrel
halide
perovskite
semiconductors,
MATtX3
(MA
=
CH3NH3+;
Tt
Ge,
Sn,
Pb;
X
Cl,
Br,
I),
arises
as
a
result
non-covalent
interactions
between
an
organic
cation
(CH3NH3+)
and
inorganic
anion
(TtX3−).
However,
basic
understanding
underlying
chemical
bonding
in
these
systems
that
link
ionic
moieties
together
complex
configurations
is
still
limited.
In
this
study,
ion
pair
models
constituting
ions
were
regarded
repeating
units
periodic
crystal
density
functional
theory
simulations
performed
to
elucidate
nature
them.
It
demonstrated
not
only
charge-assisted
N–H···X
C–H···X
hydrogen
bonds
but
also
C–N···X
pnictogen
interact
stabilize
pairs
define
their
geometries
gas
phase.
Similar
are
responsible
for
formation
crystalline
low-temperature
phase,
some
which
have
been
delineated
previous
studies.
contrast,
Tt···X
interactions,
hidden
coordinate
crystals,
play
vital
role
holding
anionic
(TtX3−)
together.
We
each
[CH3NH3+•TtX3−]
has
capacity
donate
three
(σ-hole)
halides
nearest
neighbor
TtX3−
units,
thus
causing
emergence
infinite
array
3D
TtX64−
octahedra
TtX44−
corner-shared
form
cage-like
frameworks
host
cation,
leading
materials
outstanding
optoelectronic
properties
solid
state.
harnessed
results
using
quantum
atoms
molecules,
natural
bond
orbital,
molecular
electrostatic
surface
potential
independent
gradient
validate
conclusions.
ChemistrySelect,
Journal Year:
2023,
Volume and Issue:
8(32)
Published: Aug. 23, 2023
Abstract
The
geometries
of
nitromethane‐carbonyl
dimers
were
investigated
comprehensively
with
formaldehyde,
acetaldehyde
and
acetone
as
model
Lewis
bases.
Pnicogen
bonding
involving
nitrogen
nitromethane
was
discerned
to
be
a
stabilizing
interaction
along
hydrogen
tetrel
(carbon)
interactions
in
all
these
dimers.
structures
the
generated
at
low
temperatures
under
isolated
conditions
established
using
infrared
spectroscopy
aid
ab
initio
DFT
computations.
existence
C−H⋅⋅⋅O
hydrogen,
O=N⋅⋅⋅O,
O=N⋅⋅⋅π
pnicogen
O=C⋅⋅⋅O
asserted
from
Quantum
Theory
Atoms
In
Molecules
(QTAIM),
Natural
Bond
Orbital
(NBO),
Electrostatic
Potential
(ESP)
mapping
Non‐Covalent
Interaction
(NCI)
analyses.
Methyl
substitution
on
formaldehyde
results
instigation
steric
effect
which
found
have
profound
influence
heterodimers
nitromethane‐acetaldehyde
nitromethane‐acetone.
plausible
role
probed
through
analysis
nature
dimer
systems.
