Advanced Functional Materials,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Nov. 17, 2024
Abstract
Stimuli‐responsive
materials
have
been
applied
for
sensor
devices
because
they
can
transform
and
amplify
various
target
stimuli
into
observable
signals.
Much
effort
has
devoted
to
exploring
effective
molecular
designs
obtaining
stimuli‐responsive
behaviors
by
taking
advantage
of
the
unique
optoelectronic
properties
π‐conjugated
molecules
involving
elements.
This
study
focuses
on
modulation
electronic
state
scaffolds
oxidation
number
change
hypervalent
antimony.
demonstrate
that
strength
intramolecular
interaction
between
antimony
framework
be
tuned
with
ligand
structure,
substituent
effect,
shifts
In
particular,
color
changes
represented
hypsochromic
bathochromic
wavelength
optical
bands
are
achieved
oxidative
reaction
in
solid
state.
Significantly,
direction
confidently
predicted
quantum
chemical
calculations.
The
findings,
based
main‐group
elements,
provide
logical
design
strategies
advanced
materials.
Accounts of Chemical Research,
Journal Year:
2024,
Volume and Issue:
57(3), P. 362 - 374
Published: Jan. 26, 2024
ConspectusAmong
the
noncovalent
interactions
available
in
toolbox
of
crystal
engineering,
chalcogen
bonding
(ChB)
has
recently
entered
growing
family
σ-hole
interactions,
following
strong
developments
based
on
halogen
(XB)
interaction
over
last
30
years.
The
monovalent
character
halogens
provides
directionality
and
strength.
Combined
with
extensive
organic
chemistry
Br
I
derivatives,
it
led
to
many
applications
XB,
solution
(organo-catalysis,
anion
recognition
transport),
solid
state
(cocrystals,
conducting
materials,
fluorescent
topochemical
reactions,
...),
soft
matter
(liquid
crystals,
gels,···),
biochemistry.
presence
two
σ-holes
divalent
chalcogens
ability
activate
them,
as
electron-withdrawing
groups
(EWG)
fueled
more
recent
interest
bonding.
However,
despite
being
identified
for
years,
ChB
still
struggles
make
a
mark
due
(i)
underdeveloped
synthetic
heavier
Se
Te;
(ii)
limited
stability
chalcogenides,
especially
tellurides;
(iii)
poor
predictability
associated
σ-holes.
It
therefore
invites
great
deal
attention
molecular
chemists
design
develop
selected
donors,
scrutiny
fundamentals
their
successful
use
different
applications.
This
Account
aims
summarize
our
own
contributions
this
direction
that
extend
from
fundamental
studies
focused
addressing
lack
directionality/predictability
systematic
demonstration
its
potential,
specifically
particularly
toward
anionic
networks
one
hand,
reactions
other
hand.In
Account,
we
share
results
aimed
at
recovering
same
degree
strength
found
by
focusing
Te
systems
substituents,
them
an
EWG,
strongly
unbalance
both
For
purpose,
explored
dissymmetrization
concept
within
three
chemical
families,
selenocyanates
R–SeCN,
alkynyl
derivatives
R–C≡C–(Se/Te)Me,
o-carborane
derivatives.
Such
compounds
were
systematically
engaged
cocrystals
either
halides
or
neutral
bipyridines
acceptors,
revealing
potential
chelate
well
organize
reactive
molecules
such
alkenes
butadiynes
[2+2]
cycloadditions
polydiacetylene
formation,
respectively.
selective
activation
is
not
but
can
be
effectively
used
all
(pnictogen
bond,
tetrel
etc.)
where
needs
control
interaction.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(28)
Published: April 26, 2024
Intermolecular
pnictogen
bonding
(PnB)
catalysis
has
received
increased
interest
in
non-covalent
organocatalysis.
It
been
demonstrated
that
organic
electron-deficient
atoms
can
act
as
prospective
Lewis
acids.
Here,
we
present
a
catalytic
approach
for
the
asymmetric
synthesis
of
chiral
P
Chemistry - A European Journal,
Journal Year:
2024,
Volume and Issue:
30(27)
Published: Feb. 29, 2024
Abstract
A
bidentate
boron
Lewis
acid
based
on
1,8‐diethynylanthracene
has
been
studied
in
detail
with
respect
to
its
adduct
formation
diamines
and
diphosphanes
of
different
linker
lengths
between
the
donor
functions.
clear
correlation
length
bifunctional
base
1
:
adducts,
2
adducts
or
oligomers
was
found.
The
were
characterized
solution
by
NMR
titration
experiments
structurally
X‐ray
diffraction.
In
addition,
competition
host
system
ZR
3
(Z=N,
P;
R=H,
Me)
demonstrated
generally
higher
stability
alkylphosphane
compared
alkylamine
results
provide
a
general
insight
into
acids
guests
sizes
as
well
differences
borane‐amine
borane‐phosphane
adducts.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(30), P. 12118 - 12125
Published: Jan. 1, 2024
(F
5
C
2
)
SbCH
P(
t
Bu)
reacts
in
a
FLP-like
manner
with
CS
,
SO
PhNCO/S
and
(MePh
P)AuCl.
The
AuCl
adduct
show
secondary
interactions
between
the
Lewis
acidic
Sb
atom
electron
rich
atoms,
intra-
intermolecular,
respectively.
Chemical Science,
Journal Year:
2023,
Volume and Issue:
14(46), P. 13551 - 13559
Published: Jan. 1, 2023
A
tetradentate
host
system
with
four
CC–Sb(C
2
F
5
)
functions
binds
halide
ions
in
a
distorted
square
planar
coordination.
Experimental
and
calculated
structures
reveal
complex
interplay
of
attractive
pnictogen
bonding
Coulomb
repulsion.
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.
Inorganic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: May 25, 2025
Differences
in
the
chemical
properties
of
phosphorus
and
antimony
enable
synthesis
heteroditopic
derivatives
whose
can
be
modified
by
altering
pnictogen
substituents.
In
this
work,
1-(diphenylstibino)-2-(dicyclohexylphosphino)ferrocene,
[Fe(η5-1-Ph2Sb-2-Cy2PC5H3)(η5-C5H5)]
(1),
corresponding
phosphine
chalcogenides
[Fe(η5-1-Ph2Sb-2-Cy2P(E)C5H3)(η5-C5H5)]
(E
=
O,
S,
Se)
catecholatostiboranes
[Fe(η5-1-Ph2(Cl4C6O2)Sb-2-Cy2P(E)C5H3)(η5-C5H5)]
void,
were
examined,
with
a
focus
on
intramolecular
donor-acceptor
interactions
between
Experimental
data
theoretical
analysis
consistently
indicated
that
these
described
as
bonding
Lewis
acidic
lone
pair
at
substituent
(either
or
chalcogen
atom)
they
are
significantly
stronger
stiboranes
due
to
increased
acidity
Sb
atom.
Noncovalent
also
observed
chlorogold(I)
complexes
obtained
from
1
catecholatostiborane
[Fe(η5-1-Ph2(Cl4C6O2)Sb-2-Cy2PC5H3)(η5-C5H5)]
P-donors.
As
shown
experiments
Au-mediated
cyclization
N-propargylbenzamide,
noncoordinated
group
influenced
catalytic
Au(I)
complexes.
Notably,
an
Cl
→
bond
affected
molecular
geometry
Pd(II)
complex
[PdCl2(1-κ2P,Sb)],
which
turn
suggested
structural
influence
exerted
ligands
type
needs
assessed
care.
Chemistry - A European Journal,
Journal Year:
2024,
Volume and Issue:
30(39)
Published: May 14, 2024
Chalice-shaped
tridentate
poly-Lewis
acids
(PLA)
based
on
the
tribenzotriquinacene
(TBTQ)
scaffold
have
been
synthesised.
Stannylation
of
alkyne
units,
attached
via
phenyl-spacers
to
benzhydrylic
positions
TBTQ
scaffold,
with
Me
International Journal of Molecular Sciences,
Journal Year:
2023,
Volume and Issue:
24(22), P. 16193 - 16193
Published: Nov. 10, 2023
In
recent
years,
the
non-covalent
interactions
between
chalcogen
centers
have
aroused
substantial
research
interest
because
of
their
potential
applications
in
organocatalysis,
materials
science,
drug
design,
biological
systems,
crystal
engineering,
and
molecular
recognition.
However,
studies
on
π-hole-type
chalcogen∙∙∙chalcogen
are
scarcely
reported
literature.
Herein,
intermolecular
model
complexes
formed
XO2
(X
=
S,
Se,
Te)
CH3YCH3
(Y
O,
were
systematically
studied
by
using
quantum
chemical
computations.
The
stabilized
via
one
primary
X∙∙∙Y
bond
(ChB)
secondary
C-H∙∙∙O
hydrogen
bonds.
binding
energies
range
-21.6~-60.4
kJ/mol.
distances
significantly
smaller
than
sum
van
der
Waals
radii
corresponding
two
atoms.
ChBs
all
except
for
SO2∙∙∙CH3OCH3
complex
strong
strength
display
a
partial
covalent
character
revealed
conducting
theory
atoms
molecules
(QTAIM),
interaction
plot
(NCIplot),
natural
orbital
(NBO)
analyses.
symmetry-adapted
perturbation
(SAPT)
analysis
discloses
that
primarily
dominated
electrostatic
component.