Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(49)
Опубликована: Сен. 13, 2023
We
here
disclose
that
the
incorporation
of
thiophene
rings
into
a
seven-membered
8π
azepine
in
fused
fashion
produces
useful
antiaromatic
core
for
near-infrared
(NIR)
dyes.
In
contrast
to
dibenzazepine
derivatives
with
bent
structures,
dithieno-fused
electron-accepting
groups
adopt
flat
conformations
ground
state.
The
exhibited
broad
absorption
spectra
cover
visible
region
as
well
sharp
emission
bands
NIR
region,
which
are
considerably
red-shifted
relative
those
dibenzo-fused
congeners.
Theoretical
study
revealed
two
contradictory
effects
less-aromatic
thiophene-fused
structure,
i.e.,
enhancement
antiaromaticity
adjacent
ring
and
relief
through
contribution
quinoidal
resonance
form.
combination
dithienoazepine
cationic
produced
fluorescent
dye
an
at
878
nm
solution.
Chemical Society Reviews,
Год журнала:
2023,
Номер
52(4), С. 1331 - 1381
Опубликована: Янв. 1, 2023
A
comprehensive
summary
and
deep
insights
into
the
synthesis,
characterization
multi-functional
device
applications
of
n-type
ambipolar
organic
semiconductors
are
provided
in
this
study.
Advanced Materials,
Год журнала:
2023,
Номер
35(18)
Опубликована: Фев. 23, 2023
Double-cable
conjugated
polymers
with
pendent
electron
acceptors,
including
fullerene,
rylene
diimides,
and
nonfused
have
been
developed
for
application
in
single-component
organic
solar
cells
(SCOSCs)
efficiencies
approaching
10%.
In
this
work,
Y-series
acceptors
firstly
incorporated
into
double-cable
order
to
further
improve
the
of
SCOSCs.
A
highly
crystalline
acceptor
based
on
quinoxaline
core
random
copolymerized
strategy
are
used
optimize
ambipolar
charge
transport
nanophase
separation
polymers.
As
a
result,
an
efficiency
13.02%
is
obtained
polymer,
representing
highest
performance
SCOSCs,
while
regular
polymer
only
provides
low
2.75%.
The
significantly
enhanced
attributed
higher
carrier
mobilities,
better
ordering
backbones
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(17), С. 9886 - 9894
Опубликована: Апрель 21, 2023
Two
[n]heliceno-bis(naphthalimides)
1
and
2
(n
=
5
6,
respectively)
where
two
electron-accepting
naphthalimide
moieties
are
attached
at
both
ends
of
helicene
core
were
synthesized
by
effective
two-step
strategy,
their
enantiomers
could
be
resolved
chiral
stationary-phase
high-performance
liquid
chromatography
(HPLC).
The
single-crystal
X-ray
diffraction
analysis
enantiopure
fractions
confirmed
helical
structure,
together
with
experimental
calculated
circular
dichroism
(CD)
spectra,
the
absolute
configuration
was
unambiguously
assigned.
Both
exhibit
high
molar
extinction
coefficients
for
S0–S1
transition
fluorescence
quantum
yields
(73%
69%
2),
being
outstanding
derivatives.
red
circularly
polarized
luminescence
(CPL)
emission
up
to
615
nm
CPL
brightness
(BCPL)
66.5
M–1
cm–1
demonstrates
its
potential
applications
in
optoelectronics.
Time-dependent
density
functional
theory
(TD-DFT)
calculations
showed
that
large
magnetic
dipole
moment
|m|
is
responsible
absorbance
dissymmetry
(gabs)
(glum)
factor.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(18), С. 10092 - 10103
Опубликована: Апрель 26, 2023
Highly
emissive
π-conjugated
macrocycles
with
tunable
circularly
polarized
luminescence
(CPL)
have
sparked
theoretical
and
synthetic
interests
in
recent
years.
Herein,
we
report
a
approach
to
obtain
new
chiral
organoborane
(CMC1,
CMC2,
CMC3)
that
are
built
on
the
structurally
[5]helicenes
highly
luminescent
triarylborane/amine
moieties
embedded
into
cyclic
systems.
These
rarely
accessible
B/N-doped
main-group
show
unique
topology
dependence
of
optoelectronic
chiroptical
properties.
CMC1
CMC2
higher
dissymmetry
factor
(glum)
together
an
enhanced
CPL
brightness
(BCPL)
as
compared
CMC3.
Electronic
effects
were
also
tuned
resulted
bathochromic
shifts
their
emission
responses
from
blue
for
near-infrared
(NIR)
region
Furthermore,
chemical
oxidations
N
donor
sites
gave
rise
stable
radical
cation
(CMC1·+SbF6–)
diradical
dication
species
(CMC12·2+2SbF6–)
serve
rare
example
positively
charged
open-shell
macrocycle.
Chemical Society Reviews,
Год журнала:
2024,
Номер
53(13), С. 6960 - 6991
Опубликована: Янв. 1, 2024
This
review
meticulously
traces
the
development
of
film-based
fluorescent
sensors,
spotlighting
key
advancements
in
molecular
design
and
film
structural
engineering.
ACS Catalysis,
Год журнала:
2025,
Номер
15(3), С. 1829 - 1840
Опубликована: Янв. 17, 2025
Perylene
diimides
(PDIs)
and
their
derivatives
represent
a
kind
of
most
promising
photocatalytic
materials
due
to
strong
visible
light
absorption,
ease
functionalization,
excellent
thermal/photostability,
as
well
tunable
electronic
structures
energy
levels.
However,
several
challenges
persist
in
the
development
PDI
photocatalysts,
including
low
electron–hole
separation
efficiency,
slow
charge
transfer,
rapid
carrier
recombination.
In
this
perspective,
we
focus
on
enhancing
performance
photocatalysts
through
molecular
design.
We
provide
comprehensive
overview
various
improvement
strategies:
(1)
precise
modulation
dipole
moments
by
altering
polarity
side
chains
strengthen
built-in
electric
field,
(2)
utilization
steric
hindrance
noncovalent
interactions
construct
nanoscale,
highly
ordered
supramolecular
nanostructures,
(3)
modification
perylene
core
adjust
levels
increase
number
active
sites,
(4)
integration
with
semiconductors
or
metals
form
composite
systems
that
enhance
interfacial
field
create
extensive
delocalized
channels,
(5)
selection
suitable
linker
groups
build
polymer
large
moments.
These
strategies
can
facilitate
migration
photogenerated
carriers
eventually
boosting
efficiency.
The
relationship
between
structure
performance,
particularly
context
degradation
water
splitting,
is
examined
detail.
Finally,
future
prospects
are
thoroughly
discussed.
ACS Nano,
Год журнала:
2023,
Номер
17(21), С. 20734 - 20752
Опубликована: Окт. 27, 2023
The
creation
and
development
of
carbon
nanomaterials
promoted
material
science
significantly.
Bottom-up
synthesis
has
emerged
as
an
efficient
strategy
to
synthesize
atomically
precise
nanomaterials,
namely,
molecular
carbons,
with
various
sizes
topologies.
Different
from
the
properties
feasibly
obtained
mixture
numerous
single-component
carbons
have
been
discovered
owing
their
well-defined
structures
well
potential
applications
in
fields.
This
Perspective
introduces
recent
advances
derived
fullerene,
graphene,
nanotube,
carbyne,
graphyne,
Schwarzite
acquired
different
strategies.
By
selecting
a
variety
representative
examples,
we
elaborate
on
relationship
between
nanomaterials.
We
hope
these
multiple
points
view
presented
may
facilitate
further
advancement
this
field.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(18)
Опубликована: Март 6, 2023
We
herein
present
the
synthetic
approach
to
a
new
antiaromatic
double
aza[7]helicene
C
that
features
NN-embedded
polycyclic
aromatic
hydrocarbons
(PAHs).
This
heteroatom-doped
helicene
showed
rarely
obtained
long-wavelength
emission
and
far-red
circularly
polarized
luminescence
(CPL)
in
solid
state.
These
optical
chiroptical
properties
could
be
ascribed
both
NN-PAH
core
structure
further
extension
through
angular
ring
fusions.
Such
unique
electronic
also
culminated
facile
chemical
oxidations
of
neutral
positively
charged
chiral
radical
(C⋅+
)
dication
species
(C2+
).
Interestingly,
DFT
computations
revealed
pyridazine
central
an
antiaromaticity-to-aromaticity
switching,
contrast
inversed
transition
for
helical
periphery
cationic
states.
The
reported
approaches
are
anticipated
lead
development
redox-active
systems
potential
applications
chiroptoelectronics,
spintronics
as
well
fluorescent
bioimaging.
Advanced Functional Materials,
Год журнала:
2023,
Номер
33(22)
Опубликована: Фев. 26, 2023
Abstract
Currently,
n‐type
small‐molecule
mixed
ionic‐electronic
conductors
remain
less
explored
and
their
molecular
design
rules
are
not
mature
enough.
Herein,
two
glycolated
imide‐fused
polycyclic
aromatic
hydrocarbons
(IPAHs),
d‐gdiPDI
t‐gdiPDI,
developed
to
probe
the
effects
of
conformation
on
electronic,
electrochemical,
morphological,
coupled
transport
properties.
It
is
found
that
highly
twisted
scaffold
in
d‐gdiPDI,
compared
nearly
planar
one
has
a
strong
positive
effect
charge
storage
properties
thus
performance
organic
electrochemical
transistors
(OECTs).
exhibits
volumetric
capacitance
657
F
cm
−3
,
obviously
outperforming
t‐gdiPDI
(261
),
which
highest
value
reported
date
for
OECT
materials.
Moreover,
high
charge‐storage
capacity
up
479
g
−1
observed
d‐gdiPDI.
Arising
from
such
coupling
characteristic,
d‐gdiPDI‐based
OECTs
present
≈2
×
times
higher
geometry‐normalized
transconductance
(
m,norm
)
105.3
mS
relative
counterparts.
Significantly,
further
application
solid‐electrolyte
delivers
142.4
.
These
findings
indicate
IPAHs
very
promising
candidates
highlight
superiority
twisting
manipulation
materials
toward
high‐performance
devices.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(49), С. 26824 - 26832
Опубликована: Дек. 4, 2023
Helical
nanographenes
(NGs)
have
attracted
increasing
attention
recently
because
of
their
intrinsic
chirality
and
exotic
chiroptical
properties.
However,
the
efficient
synthesis
extended
helical
NGs
featuring
a
multilayer
topology
is
still
underdeveloped,
layer-dependent
properties
remain
elusive.
In
this
study,
we
demonstrate
modular
synthetic
strategy
to
construct
series
novel
(1-3)
with
through
consecutive
Diels-Alder
reaction
regioselective
cyclodehydrogenation
from
readily
accessible
phenanthrene-based
precursors
bearing
ethynyl
groups.
The
resultant
exhibit
bilayer,
trilayer,
tetralayer
structures
elongated
π
extension
rigid
backbones,
as
unambiguously
confirmed
by
single-crystal
X-ray
or
electron
diffraction
analysis.
We
find
that
photophysical
these
are
notably
influenced
degree
extension,
which
varies
number
layers,
leading
obvious
redshifted
absorption,
fast
rising
molar
extinction
coefficient
(ε),
markedly
boosted
fluorescence
quantum
yield
(Φf).
Moreover,
embedded
[7]helicene
subunits
in
result
stable
chirality,
enabling
both
chiral
resolution
exploration
Profiting
good
alignment
electric
magnetic
dipole
moments
determined
structure,
excellent
circular
dichroism
circularly
polarized
luminescence
response
unprecedented
high
CPL
brightness
up
168
M-1
cm-1,
rendering
them
promising
candidates
for
emitters.