Angewandte Chemie,
Год журнала:
2023,
Номер
135(36)
Опубликована: Июль 7, 2023
Abstract
Acepleiadylene
(APD),
a
nonbenzenoid
isomer
of
pyrene,
exhibits
unique
charge‐separated
character
with
large
molecular
dipole
and
small
optical
gap.
However,
APD
has
never
been
explored
in
optoelectronic
materials
to
take
advantage
these
appealing
properties.
Here,
we
employ
as
building
block
organic
semiconducting
for
the
first
time,
unravel
superiority
electronic
applications.
We
have
synthesized
an
derivative
(APD‐IID)
terminal
donor
moieties
isoindigo
(IID)
acceptor
core.
Theoretical
experimental
investigations
reveal
that
APD‐IID
obvious
structure
enhanced
intermolecular
interactions
compared
its
pyrene‐based
isomers.
As
result,
displays
significantly
higher
hole
mobilities
than
those
counterparts.
These
results
imply
advantages
employing
great
potential
polycyclic
arenes
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(11)
Опубликована: Янв. 17, 2024
Abstract
We
report
a
unique
category
of
π‐extended
diaza[7]helicenes
with
double
negative
curvatures.
This
is
achieved
by
two‐fold
regioselective
heptagonal
cyclization
the
oligoarylene‐carbazole
precursors
through
either
intramolecular
C−H
arylation
or
Scholl
reaction.
The
fusion
two
rings
in
helical
skeleton
dramatically
increases
strain
and
forces
terminal
carbazole
moieties
to
stack
compressed
fashion.
presence
deformable
negatively
curved
endows
resulting
dynamic
chiral
skeletons,
aggregation‐induced
emission
feature
relatively
low
racemization
barrier
ca.
25.6
kcal
mol
−1
.
Further
π‐extension
on
subsequently
leads
more
sophisticated
C
2
‐symmetric
homochiral
triple
helicene.
Notably,
these
show
structure‐dependent
stacking
upon
crystallization,
switching
from
heterochiral
packing
intra‐layer
stacking.
Interestingly,
helicene
molecules
spontaneously
resolve
into
lamellar
structure
3
1
helix
symmetry.
Upon
ultrasonication
nonsolvent,
crystals
can
be
readily
exfoliated
large‐area
ultrathin
nanosheets
height
4.4
nm
corresponding
layers
stacked
thicker
constituted
even‐numbered
molecular
lamellae.
Moreover,
regular
hexagonal
thin
platelets
size
larger
than
30
μm
fabricated
flash
aggregation.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(9)
Опубликована: Янв. 10, 2024
We
report
the
helicoselective
and
convergent
construction
of
indolohelicenoids
with
excellent
efficiency
stereocontrol.
This
reaction
proceeds
through
a
chiral-phosphoric-acid-catalyzed
enantioselective
cycloaddition
eliminative
aromatization
sequence,
which
can
be
finely
controlled
by
adjusting
temperature.
Mechanistic
studies
reveal
that
chiral
phosphoric
acid
cooperatively
serves
as
both
bifunctional
Brønsted
catalyst,
enabling
one-pot
central-to-helical
chirality
conversion.
Additionally,
optical
properties
synthesized
were
characterized
to
explore
their
potential
applications
in
organic
photoelectric
materials.
Asian Journal of Organic Chemistry,
Год журнала:
2023,
Номер
12(12)
Опубликована: Ноя. 21, 2023
Abstract
Atomic
precise
chiral
molecules
with
all‐hydrocarbon
backbones,
such
as
helicenes
and
related
π‐extended
derivatives,
attract
critical
interests
due
to
their
great
application
potential
in
many
fields
(e.
g.,
optical
materials,
asymmetric
catalysis,
molecular
machines).
Herein,
the
main
development
of
these
past
decade
was
summarizes,
including
enantioselective
synthesis
helicenes,
helicene
extension
along
perpendicular
helical
axis,
well
following
both
directions,
namely
helix
axis
direction.
Macromolecules,
Год журнала:
2024,
Номер
57(3), С. 991 - 1000
Опубликована: Янв. 24, 2024
Ladder
polymers
with
backbones
of
uninterrupted
ring-fused
units
have
attracted
academic
and
industrial
attention
for
decades
because
their
extended
π-conjugation
intrinsic
microporosity
possible
potential
applications
in
organic
optoelectronics
membrane
gas
separations.
We
report
herein
the
synthesis
characterization
a
new
series
oxepine-based
ladder/step-ladder
prepared
by
acid-promoted
intramolecular
aromatic
electrophilic
cyclization
reactions
on
alkyne-containing
poly(arylene
ether)
precursors.
In
contrast
to
more
common
annulations
that
produce
five-
six-membered
rings,
we
seven-membered
ring
can
be
regioselectively
quantitatively
generated
postpolymerization.
Model
compounds
repeating
also
been
synthesized,
X-ray
crystallographic
analysis
reveals
nonplanar
contorted
structure
is
present
polymers.
More
interestingly,
appear
display
photoinduced
planarization
8
π
electron
oxepine
driven
excited-state
stabilization
energy,
as
indicated
large
Stokes
shift.
Chemical Science,
Год журнала:
2024,
Номер
15(15), С. 5516 - 5524
Опубликована: Янв. 1, 2024
The
Curtin–Hammett
principle
is
used
to
understand
the
diastereoselective
synthesis
of
a
heterochiral
over
homochiral
macrocycle,
both
which
are
configurationally
stable
chiral
macrocycles.
We
report
here
a
cascade
process
integrating
the
hexadehydro
Diels-Alder
(HDDA)
reaction
with
alkynyliodanation,
enabling
efficient
synthesis
of
highly
substituted
aryl-λ3-iodanes.
Heating
mixture
tetrayne
and
an
alkynylbenziodoxole
induces
regioselective
insertion
tetrayne-derived
aryne
into
alkynyl-iodine(III)
bond,
yielding
1,4-dialkynyl-2-iodanyl-3-aryl(or
alkyl)benzene
derivative.
The
unique
regiochemistry
facilitates
subsequent
π-extension,
allowing
divergent
access
to
polyaromatic
frameworks,
such
as
helicenes
cyclopenta[cd]pyrenes,
underscoring
utility
carboiodanation
in
complex
aromatic
synthesis.
Chemical Science,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
Axially
chiral
substrates
were
transformed
into
enantiomer-enriched
π-extended
helicenes
via
a
chiral-transfer-based
Scholl
reaction,
and
enantiomers
efficiently
separated
without
labor-intensive
high-performance
liquid
chromatography
(HPLC).
Organic & Biomolecular Chemistry,
Год журнала:
2024,
Номер
22(16), С. 3186 - 3197
Опубликована: Янв. 1, 2024
This
review
showcases
a
systematic
overview
of
the
available
tools
for
catalytic
asymmetric
transformation
biaryl
substrates
toward
construction
challenging
enantioenriched
helicenes
and
conceptual
aspects
associated
with
each
type
transformation.
Depending
on
properties
nature
process,
several
methodologies
have
been
developed,
including
olefin
metathesis,
hydroarylation
alkynes,
C-X
(X
=
C,
O,
N)
coupling,
C-H
functionalization.
Pioneering
studies
an
array
representative
reactions
are
discussed
to
underscore
potential
these
synthetic
protocols.
Chemistry - A European Journal,
Год журнала:
2023,
Номер
29(48)
Опубликована: Июнь 7, 2023
A
nitrogen-centered
heptalene,
azaheptalene,
was
designed
as
a
representative
of
new
class
redox-responsive
molecules
with
large
steric
strain
that
originates
from
the
adjacent
seven-membered
rings.
The
pentabenzo
derivative
azaheptalene
efficiently
synthesized
by
palladium-catalyzed
one-pot
reaction
commercially
available
reagents.
Bromination
led
to
mono-
and
dibrominated
derivatives,
latter
which
is
interconvertible
isolable
radical
cation
species
exhibiting
near-infrared
absorption.
Since
skeleton
shows
configurationally
stable
helicity
torsion
angle,
enantiomers
could
be
successfully
separated.
Thus,
optically
pure
azaheptalenes
P-
or
M-helicity
showed
strong
chiroptical
properties
(|gabs
|≥0.01),
changed
an
electric
potential.
