Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(19), С. 13499 - 13508
Опубликована: Май 2, 2024
Near-infrared
(NIR)
circularly
polarized
light
absorbing
or
emitting
holds
great
promise
for
highly
sensitive
and
precise
bioimaging,
biosensing,
photodetectors.
Aiming
at
designing
NIR
chiral
molecular
systems
with
amplified
dissymmetry
robust
chiroptical
response,
herein,
we
present
a
series
of
double
π-helical
dimers
longitudinally
extended
π-entwined
substructures
via
Ullmann
Yamamoto
homocoupling
reactions.
Circular
dichroism
(CD)
spectra
revealed
an
approximate
linear
bathochromic
shift
the
rising
number
naphthalene
subunits,
indicating
red
to
response.
Particularly,
terrylene
diimide-entwined
exhibited
strongest
CD
intensities,
maximal
|Δε|
reaching
up
393
M–1
cm–1
666
nm
th-TDI[2];
record-high
response
(|ΔΔε|)
between
neutral
dianionic
species
520
833
th-TDI[2]Cl
was
achieved
upon
further
reduction
its
state.
Time-dependent
density
functional
theory
(TDDFT)
calculations
suggested
that
pronounced
intensification
originated
from
simultaneous
enhancement
both
electric
(μ)
magnetic
(m)
transition
dipole
moments,
ultimately
leading
overall
increase
in
rotatory
strength
(R).
Notably,
luminescence
(CPL)
brightness
(BCPL)
reached
77
th-TDI[2]Cl,
among
highest
values
reported
NIR-CPL
emitters.
Furthermore,
all
dianions
excellent
air
stability
under
ambient
conditions
half-life
times
10
days
N-methylpyrrolidone
(NMP),
which
is
significant
future
biological
applications
chiroptic
switches.
Advanced Materials,
Год журнала:
2023,
Номер
36(5)
Опубликована: Сен. 12, 2023
Chiral
B/N
embedded
multi-resonance
(MR)
emitters
open
a
new
paradigm
of
circularly
polarized
(CP)
organic
light-emitting
diodes
(OLEDs)
owing
to
their
unique
narrowband
spectra.
However,
pure-red
CP-MR
and
devices
remain
exclusive
in
literature.
Herein,
by
introducing
B-N
covalent
bond
lower
the
electron-withdrawing
ability
para-positioned
B-π-B
motif,
first
pair
double
hetero-[n]helicenes
(n
=
6
7)
emitter
peaking
617
nm
with
small
full-width
at
half-maximum
38
high
photoluminescence
quantum
yield
≈100%
toluene
is
developed.
The
intense
mirror-image
CP
light
produced
enantiomers
characterized
dissymmetry
factors
(g
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(32)
Опубликована: Май 13, 2024
Abstract
Circularly
polarized
luminescence
(CPL)
is
promising
for
applications
in
many
fields.
However,
most
systems
involving
CPL
are
within
the
visible
range;
near‐infrared
(NIR)
CPL‐active
materials,
especially
those
that
exhibit
high
g
lum
values
and
can
be
controlled
spatially
temporally,
rare.
Herein,
dynamic
NIR‐CPL
with
a
value
of
2.5×10
−2
was
achieved
through
supramolecular
coassembly
energy‐transfer
strategies.
The
chiral
assemblies
formed
by
between
adenosine
triphosphate
(ATP)
pyrene
derivative
exhibited
red
signal
(
10
−3
).
further
introduction
sulfo‐cyanine5
resulted
process,
which
not
only
led
to
NIR
but
also
increased
.
Temporal
control
these
realized
introducing
alkaline
phosphatase
fabricate
biomimetic
enzyme‐catalyzed
network,
allowing
turned
on.
Based
on
enzyme‐regulated
temporally
controllable
assemblies,
multilevel
information
encryption
system
developed.
This
study
provides
pioneering
example
construction
materials
ability
perform
temporal
via
assembly
strategy,
expected
aid
design
complex
more
closely
resemble
natural
biological
systems.
Chemical Communications,
Год журнала:
2023,
Номер
59(88), С. 13089 - 13106
Опубликована: Янв. 1, 2023
This
review
comprehensively
summarizes
circularly
polarized
luminescence
materials
from
chiral
macrocycles,
especially
macrocyclic
hosts
and
their
derivatives.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(8), С. 5295 - 5304
Опубликована: Фев. 16, 2024
Unveiling
the
mechanism
behind
chirality
propagation
and
dissymmetry
amplification
at
molecular
level
is
of
significance
for
development
chiral
systems
with
comprehensively
outstanding
chiroptical
performances.
Herein,
we
have
presented
a
straightforward
Cu-mediated
Ullmann
homocoupling
approach
to
synthesize
perylene
diimide-entwined
double
π-helical
nanoribbons
encompassing
dimer,
trimer,
tetramer
while
producing
homochiral
or
heterochiral
linking
centers.
A
significant
was
achieved,
absorption
factors
(|gabs|)
increasing
from
0.009
0.017
further
0.019,
luminescence
(|glum|)
rising
0.007
0.013
eventually
0.015
oligomers.
The
disparity
magnetic
transition
dipole
moment
(m)
densities
in
tetramers
by
time-dependent
density
functional
theory
calculations
confirmed
that
oligomerization
can
maximize
total
m,
which
favorable
achieving
ever-increasing
g
factors.
Notably,
these
π-helices
exhibited
exceptional
photoluminescence
quantum
yields
(ΦPL)
ranging
83
95%.
circularly
polarized
brightness
(BCPL)
reached
remarkable
575
M–1
cm–1
tetramer,
among
highest
values
reported
small
molecules.
This
kind
linearly
extended
offers
platform
comprehensive
understanding
amplification.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(29)
Опубликована: Май 2, 2024
Abstract
Conjugated
molecules
with
multiple
radical
centers
such
as
the
iconic
Chichibabin
diradicaloid
hold
promise
building
blocks
in
materials
for
quantum
sensing
and
information
processing.
However,
it
is
a
considerable
challenge
to
design
simple
analogues
of
hydrocarbon
that
are
chemically
inert,
exhibit
high
diradical
character
emit
light
at
distinct
wavelength
may
offer
an
optical
readout
spin
state
functional
ensembles.
Here
we
describe
serendipitous
discovery
stable
TTM‐TTM
diradicaloid,
which
exhibits
character,
striking
sky‐blue
color
near‐infrared
(NIR)
emission
(in
solution).
This
combination
properties
unique
among
related
diradicaloids
due
presence
hydrogen
chlorine
atoms
“just
right
positions”,
allowing
perfectly
planar,
yet
predominantly
benzenoid
bridge
connect
two
sterically
stabilized
centers.
In‐depth
studies
magnetic
suggest
this
structural
motif
could
become
mainstay
block
organic
materials.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(8), С. 5470 - 5479
Опубликована: Фев. 14, 2024
Macrocycles
containing
chiral
organic
dyes
are
highly
valuable
for
the
development
of
supramolecular
circularly
polarized
luminescent
(CPL)
materials,
where
a
preorganized
framework
is
conducive
to
directing
π–π
self-assembly
and
delivering
strong
persistent
CPL
signal.
Here,
perylene
diimides
(PDIs)
an
excellent
choice
dye
component
because,
alongside
their
tunable
photophysical
properties,
functionalization
PDI's
core
yields
twisted,
π-system,
capable
CPL.
However,
configurationally
stable
PDI-based
macrocycles
rare,
those
that
also
beyond
dimers
unprecedented,
both
which
advantageous
robust
self-assembled
chiroptical
materials.
In
this
work,
we
report
first
bay-connected
bis-PDI
macrocycle
(ΔG⧧
>
155
kJ
mol–1).
We
use
chirally
locked
uncover
new
knowledge
PDI
perform
quantitative
imaging
resulting
single-crystal
As
such,
discover
chirality
1,7-disubstituted
provides
rational
route
designing
H-,
J-
concomitant
H-
J-type
important
arrangements
optimizing
(chir)optical
charge/energy
transport
properties.
Indeed,
reveal
amplified
in
single
crystals
our
by
quantifying
degree
emitted
light
circular
polarization
from
such
materials
time
using
CPL-Laser
Scanning
Confocal
Microscopy.
Advanced Optical Materials,
Год журнала:
2024,
Номер
12(18)
Опубликована: Май 20, 2024
Abstract
Molecular
chirality
plays
a
pivotal
role
across
the
disciplines
of
chemical
and
physical
sciences,
as
well
holding
significant
implications
in
realms
medicine
technology.
Chiral
macrocycles
have
attracted
recent
interests
synthetic
chemistry,
material
science,
supramolecular
chemistry.
Due
to
cyclic
arrangements
stereogenic
elements
or
special
orientations
confined
rigid
structures,
π‐conjugated
chiral
are
expected
be
highly
luminescent,
configurationally
stable,
thus
serve
develop
high‐performance
chiroptical
materials.
Given
rapid
progress
achieved
this
new
area
years,
it
is
highlight
concepts
breakthroughs.
This
minireview
will
offer
overview
wide
range
from
traditional
molecules
which
include
axially,
helically,
planar
skeletons
nanobelts
with
focus
on
structure‐function
relationship
between
unique
properties.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 20, 2025
Implanting
heteroatoms
into
organic
π-conjugated
molecules
(OCMS)
offered
a
great
opportunity
to
fine-tune
the
chemical
structures
and
optoelectronic
properties.
This
work
describes
new
family
of
1,4-azaphosphinines
with
extended
σ–π
hyperconjugations.
The
photophysical
studies
revealed
that
azaphosphinines
exhibited
narrow-band
thermally
activated
delayed
fluorescence
(TADF)
(
full
width
at
half-maximum:
26–40
nm).
According
orbital
localization
analysis
natural
bond
analysis,
effective
σ*−π*
hyperconjugation
is
believed
induce
multiple-resonance
(MR)
TADF,
which
distinct
from
p−π
conjugation-induced
MR-TADF
in
BN
systems.
Although
having
large
ΔES1–T1s
(>3.0
ev),
study
suggested
σ*−π
endowed
system
structural
vibration
favorable
for
spin-vibronic-assisted
RISC.
Having
tunable
p-centers
(lp,
O,
S,
Se,
Me+),
showed
fine-tuned
TADF.
Generally,
strong
hyperconjugations
small
ΔES1–T1s,
efficient
RISCs,
high
PLQYs.
Leveraging
on
hyperconjugations,
TADF
emission
spanned
UV-blue
green.
Particularly,
photoluminescence
quantum
yields
(74%
toluene
92%
10%
doped
PMMA).
As
proof
concept,
two
PO
center
were
applied
as
light-emitting
materials
lighting-emitting
diodes.
devices
UV-
deep-blue
EQE
10.3%.
current
us
strategy,
namely,
hyperconjugation-induced
MR-TADF,
designing
OCMs
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(27)
Опубликована: Фев. 27, 2024
π-Conjugated
chiral
nanorings
with
intriguing
electronic
structures
and
chiroptical
properties
have
attracted
considerable
interests
in
synthetic
chemistry
materials
science.
We
present
the
design
principles
to
access
new
macrocycles
(1
2)
that
are
essentially
built
on
key
components
of
main-group
electron-donating
carbazolyl
moieties
or
π-expanded
aza[7]helicenes.
Both
show
unique
molecular
conformations
a
(quasi)
figure-of-eight
topology
as
result
conjugation
patterns
2,2',7,7'-spirobifluorenyl
1
triarylamine-coupled
aza[7]helicene-based
building
blocks
2.
This
nature
redox-active,
carbazole-rich
backbones
enabled
these
be
readily
oxidized
chemically
electrochemically,
leading
sequential
production
series
positively
charged
polycationic
open-shell
cyclophanes.
Their
redox-dependent
states
resulting
multispin
polyradicals
been
characterized
by
VT-ESR,
UV/Vis-NIR
absorption
spectroelectrochemical
measurements.
The
singlet
(ΔE
Advanced Functional Materials,
Год журнала:
2024,
Номер
34(47)
Опубликована: Фев. 16, 2024
Abstract
[2.2]Paracyclophanes
([2.2]PCs)
with
substituents
at
specific
positions
possesses
planar
chirality
and
stands
as
a
promising
building
unit
for
the
development
of
chiroptical
materials
associated
polarized
light.
However,
one
easily
accessible
starting
materials,
bromo‐substituted
[2.2]PC,
shows
low
reactivity,
effective
methods
π‐extension
chiral
[2.2]PC
are
limited.
Herein,
an
method
has
established
four
substitutions
from
4,7,12,15‐tetrabromo[2.2]PC.
This
led
to
tetrakis(trimethylsilylphenyl)‐[2.2]PC
that
serves
versatile
resource
radial‐type
π‐conjugated
compounds
core.
In
this
study,
synthesizing
further
succeeded
introduction
carbazole
(
Cbz
4
‐[2.2]PC
t
BuCbz
)
investigated
their
properties
induction
ability
in
achiral
polymers.
A
thin
film
[Poly[9,9‐dioctylfluorenyl‐2,7‐diyl)‐alt‐(benzo[2,1,3]thiadiazol‐4,7‐diyl)]]
(F8BT)
3wt%
prepared
by
spin‐coating
exhibits
circularly
luminescence
(CPL)
high
dissymmetry
factor
(|
g
lum
|
=
0.01),
which
is
much
higher
than
CH
2
Cl
solution.
By
contrast,
doped
F8BT
exhibited
only
weak
CPL
properties.
addition,
these
show
facile
redox
owing
presence
units.
Furthermore,
undergoes
electropolymerization
produce
insoluble
on
electrode.