Chemical Science,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Jan. 1, 2024
A
tether-entangled
conjugated
helices
(TECHs)
concept
is
introduced
for
helical
polyaromatic
molecules.
TECHs
can
be
directly
constructed
in
enantiopure
form
with
excellent
configurational
stability
and
persistent
chiroptical
properties.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(19)
Published: Feb. 19, 2024
Helical
nanographenes
with
high
quantum
yields
and
strong
chiroptical
responses
are
pivotal
for
developing
circularly
polarized
luminescence
(CPL)
materials.
Here,
we
present
the
successful
synthesis
of
novel
π-extended
double
[7]helicenes
(ED7Hs)
where
two
helicene
units
fused
at
meta-
or
para-position
middle
benzene
ring,
respectively,
as
structural
isomers
reported
ortho-fused
ED7H.
The
geometry
these
ED7Hs
is
clearly
characterized
by
single-crystal
X-ray
analysis.
Notably,
this
class
exhibits
bright
exceeding
40
%.
Through
geometric
regulation
embedded
[7]helicene
from
ortho-,
to
para-position,
display
exceptional
amplification
in
responses.
This
enhancement
evident
a
remarkable
approximate
fivefold
increase
absorbance
dissymmetry
factors
(g
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(17), P. 12206 - 12214
Published: April 18, 2024
Chiral
nanographenes
(NGs)
have
garnered
significant
interest
as
optoelectronic
materials
in
recent
years.
While
helically
chiral
NGs
been
extensively
studied,
axially
only
witnessed
limited
examples,
with
no
prior
reports
of
nonbenzenoid
NGs.
Herein
we
report
an
nanographene
featuring
six
pentagons
and
four
heptagons.
This
compound,
denoted
2,
was
efficiently
synthesized
via
efficient
Pd-catalyzed
aryl
silane
homocoupling
reaction.
The
presence
two
bulky
3,5-di-tert-butylphenyl
groups
around
the
axis
connecting
PAH
(AHR)
segments
endows
2
atropisomeric
chirality
high
racemization
energy
barrier,
effectively
preventing
both
R-
S-enantiomers
at
room
temperature.
Optically
pure
R-2
S-2
were
obtained
by
HPLC
separation,
they
exhibit
circular
dichroism
(CD)
activity
wavelengths
up
to
660
nm,
one
longest
CD
responses
reported
for
Interestingly,
racemic
forms
a
homoconfiguration
π-dimer
crystal
lattice,
belonging
I222
space
group.
Consequently,
this
unique
structure
renders
crystals
second
harmonic
generation
(SHG)
response,
distinguishing
it
from
all
benzenoid
Moreover,
also
SHG-CD
properties.
Polymer-based
one-
and
two-dimensional
(1D-2D)
carbon
nanomaterials
are
considered
promising
microwave-absorbing
materials
(MAMs)
due
to
their
high
atomic
utilization
efficiency
tunable
microscopic/macroscopic
morphology.
The
design
of
1D-2D
through
a
facile
method
meet
the
requirements
advanced
MAMs
remains
challenge.
In
this
work,
environmentally
friendly
processing
ultrasonic
spray
ice
template
(USIT)
is
employed
fabricate
porous
based
on
Kapton-type
polyimide,
which
exhibit
intriguing
morphology
both
1D
nanowires
2D
nanosheets.
Under
subsequent
carbonization
at
700
800
°C,
obtained
inherit
original
Furthermore,
or
nanomorphology
can
be
readily
controlled
by
adjusting
concentration
precursor
solution.
For
samples
fabricated
with
lower
concentrations
(0.1%),
nanowire
structures
predominant.
Interconnected
conductive
networks
heterogeneous
interfaces
formed
intertwining
stacking
nanowires,
thereby
enhancing
conductivity
loss.
Additionally,
abundant
structure
provides
an
effective
channel
for
electromagnetic
wave
entrance,
significantly
improving
impedance
matching
ability.
results
show
that
nanowire-dominated
(700
°C
carbonization)
excellent
microwave
absorption
performance.
reflection
loss
minimum
(RLmin)
-67.2
dB
8.1
GHz
4.65
mm,
maximum
bandwidth
(<-10
dB)
7.7
3.03
mm.
Exemplified
MAMs,
USIT
strategy
has
broad
prospects,
providing
enormous
potential
various
practical
applications
bridging
gap
between
polymer
precursors
1D/2D
nanomaterials.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(30), P. 11737 - 11747
Published: Jan. 1, 2024
Enantiopure
[7]helicenes
were
utilized
as
molecular
wrenches
at
the
terminal
K-regions
of
conjugated
pyrene
nanoribbon
to
achieve
a
99.9%
conformational
population
single-handed
helical
ribbon
with
an
end-to-end
twist
171°.
Interdisciplinary materials,
Journal Year:
2024,
Volume and Issue:
3(4), P. 453 - 479
Published: May 11, 2024
Abstract
In
recent
years,
the
precisely
controlled
synthesis
of
chiral
twisted
molecular
carbons
has
emerged
as
a
forefront
topic
in
research
carbon
materials.
Molecular
refer
to
nanomaterials
synthesized
with
precision
at
atomic
level.
Through
rational
design,
rigid
and
stable
structures
can
be
synthesized.
The
exploration
field
is
key
fully
understanding
various
configurations
materials
delving
into
relationship
between
structure
design
functionality.
This
review
explores
such
nanographene,
nanobelts,
nanosheets,
graphdiyne,
etc.
It
emphasizes
role
photocyclization,
Scholl
reaction,
Diels–Alder
reactions
achieving
precise
control
discusses
range
innovative
strategies.
These
strategies
have
led
development
structures,
helical,
propeller,
Möbius
strip
configurations.
introduction
chirality,
combined
inherent
exceptional
optical
properties
nanocarbon
materials,
facilitated
creation
superior
chiroptical
performances.
advancement
driving
applications
fields
optoelectronics
optics.
Advanced Functional Materials,
Journal Year:
2024,
Volume and Issue:
34(44)
Published: July 2, 2024
Abstract
Diatomic
catalysts
(DACs),
as
a
frontier
of
research
on
atomically
dispersed
catalysts,
have
drawn
great
attention,
especially
in
electrocatalysis.
However,
most
the
current
synthetic
strategies
for
DACs
suffer
from
poor
efficiency
and
high
cost.
In
this
work,
novel
noncovalent
assembly
strategy
is
reported
efficient
synthesis
DACs.
By
aid
two
kinds
intermolecular
force,
π–π
stacking
Coulomb
forces,
pair
metal
complex
ions
with
opposite
electrical
charges
spontaneously
loaded
onto
carbon
substrate
transformed
into
diatomic
sites
via
thermal
treatment.
This
approach
shows
universal
feasibility
broad
spectrum
(Ir–Fe,
Pt–Fe,
Pt–Co,
Pt–Ni).
To
prove
practical
utility,
as‐prepared
PtFe‐DAC
deployed
oxygen
reduction
reaction
catalyst,
performing
excellent
activity
half‐wave
potential
0.935
V
(vs
RHE)
2.3
times
higher
turnover
frequency
than
that
single‐atomic
Fe‐SAC.
situ
characterization
theoretical
calculation
indicate
adjacent
Pt
could
endow
moderate
activation
molecule
Fe
by
lowering
electron
pairing
energy
well
modulation
d‐band
center
spin
states
centers
propelling
desorption
intermediates.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(45)
Published: Aug. 8, 2024
Doping
of
polycyclic
conjugated
hydrocarbons
(PCHs)
with
sulfur
atoms
is
becoming
more
and
important
as
a
means
creating
unique
functional
materials.
Recently,
thiophene-containing
multiple
helicenes
have
garnered
enormous
attention
due
to
their
intriguing
electronic
(chir)optical
properties
compared
carbohelicenes.
However,
the
efficient
synthesis
thiopyran-containing
underlying
doping
mechanisms
are
rather
unexplored.
Herein,
structural
analysis
double
[7]helicene
3
reported.
X-ray
crystallographic
reveals
its
dication
C
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Dec. 6, 2024
The
semiconductor
properties
of
nanosized
graphene
fragments,
known
as
molecular
nanographenes,
position
them
exceptional
candidates
for
next-generation
optoelectronics.
In
addition
to
their
remarkable
optical
and
electronic
features,
chiral
nanographenes
exhibit
high
dissymmetry
factors
in
circular
dichroism
circularly
polarized
luminescence
measurements.
However,
the
synthesis
enantiomerically
pure
remains
a
significant
challenge.
Typically,
these
materials
are
synthesized
racemic
form,
followed
by
separation
enantiomers
using
high-performance
liquid
chromatography
(HPLC).
While
effective,
this
method
often
requires
expensive
instrumentation,
extensive
optimization
conditions,
typically
yields
analytical
quantities
desired
samples.
An
alternative
approach
is
enantioselective
nanographenes;
however,
date,
only
two
examples
have
been
documented
literature.
work,
we
present
straightforward
chemical
resolution
helical
bilayer
nanographenes.
This
enables
effective
scalable
preparation
while
avoiding
need
HPLC.
incorporation
BINOL
core
into
polyarene
precursor
facilitates
diastereomers
through
esterification
with
camphorsulfonyl
chloride.
Following
standard
chromatographic
column,
hydrolysis
group
nanographene
precursors.
subsequent
graphitization,
achieved
Scholl
reaction,
occurs
an
enantiospecific
manner
concomitant
formation
furan
ring
heterohelicene
moiety.
absolute
configurations
final
enantiomers,
P-oxa[9]HBNG
M-oxa[9]HBNG,
determined
X-ray
diffraction.
Additionally,
electrochemical,
photophysical,
chiroptical
thoroughly
evaluated.
Chirality,
Journal Year:
2024,
Volume and Issue:
36(5)
Published: May 1, 2024
Abstract
The
adjustment
of
the
main
helical
scaffold
in
helicenes
is
a
fundamental
strategy
for
modulating
their
optical
features,
thereby
enhancing
potential
diverse
applications.
This
work
explores
influence
elongation
(n
=
5–9)
on
structural,
photophysical,
and
chiroptical
features
symmetric
oxa[
n
]helicenes.
Crystal
structure
analyses
revealed
structural
variations
with
extension,
impacting
torsion
angles,
pitch,
packing
arrangements.
Through
theoretical
investigations
using
density
functional
theory
(DFT)
calculations,
impact
extension
aromaticity,
planarity
distortion,
heightened
chiral
stability
were
discussed.
Photophysical
studied
through
spectrophotometric
analysis,
insights
gained
time‐dependent
DFT
(TD‐DFT)
calculations.
Following
resolution
via
high‐performance
liquid
chromatography
(HPLC),
properties
both
enantiomers
oxa[7]helicene
oxa[9]helicene
investigated.
A
slight
variation
]helicenes
from
[7]
to
[9]
induced
an
approximately
three‐fold
increase
dissymmetry
factors
biggest
values
of|
g
lum
|
(2.2
×
10
−3
)
compared
to|
|of
(0.8
),
findings
discussed
supported
by
TD‐DFT
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(41)
Published: July 19, 2024
Abstract
The
introduction
of
precise
pore
defects
into
nanocarbon
structures
results
in
the
emergence
distinct
physicochemical
characteristics.
However,
there
is
a
lack
research
on
non‐planar
chiral
nanographene
involving
defects.
Herein,
we
have
developed
two
analogues
to
π‐extended
pentadecabenzo[9]helicene
(
EP9H
)
containing
embedded
Each
molecules,
namely
extended
dodecabenzo[7]helicene
ED7H
;
1
or
nonabenzo[5]helicene
EN5H
2
),
exhibits
dual‐state
emission.
Significantly,
value
|
g
lum
exceptionally
high
at
1.41×10
−2
solution
and
B
CPL
as
254
M
−1
cm
.
In
PMMA
film,
8.56×10
−3
,
powder
it
5.00×10
This
study
demonstrates
that
molecules
with
exhibit
emission
properties
while
maintaining
quite
good
luminescence
properties.
It
was
distinguished
from
aggregation‐caused
quenching
(ACQ)
effect
corresponding
without
defect.
Incorporating
also
simplifies
synthesis
process
enhances
solubility
resulting
product.
These
findings
suggest
can
be
viable
approach
improve
molecules.