Journal of the American Chemical Society,
Journal Year:
2021,
Volume and Issue:
143(45), P. 19232 - 19239
Published: Nov. 8, 2021
Exciton
coupling
between
the
transition
dipole
moments
of
ordered
dyes
in
supramolecular
assemblies,
so-called
J/H-aggregates,
leads
to
shifted
electronic
transitions.
This
can
lower
excited
state
energy,
allowing
for
emission
well
into
near-infrared
regime.
However,
as
we
show
here,
it
is
not
only
energy
modifications
that
J-aggregates
provide.
A
bay-alkylated
quaterrylene
was
synthesized,
which
found
form
1,1,2,2-tetrachloroethane.
combination
superradiance
and
a
decreased
nonradiative
relaxation
rate
made
J-aggregate
four
times
more
emissive
than
monomeric
counterpart.
reduced
nonintuitive
consequence
following
180
nm
(3300
cm–1)
red-shift
comparison
absorption.
gap
law,
commonly
invoked
rationalize
increased
rates
with
increasing
wavelength,
also
contains
reorganization
term.
The
highly
suppressed
due
exciton
delocalization,
framework
law
could
therefore
reproduce
our
experimental
observations.
J-Aggregates
thus
circumvent
common
belief
lowering
energies
results
large
are
pathway
toward
organic
NIR
Advanced Materials,
Journal Year:
2021,
Volume and Issue:
34(22)
Published: Oct. 19, 2021
Abstract
Dye–dye
interactions
affect
the
optical
and
electronic
properties
in
organic
semiconductor
films
of
light
harvesting
detecting
optoelectronic
applications.
This
review
elaborates
how
to
tailor
these
semiconductors
for
solar
cells
(OSCs)
photodiodes
(OPDs).
While
devices
rely
on
similar
materials,
demands
their
are
rather
different,
former
requiring
a
broad
absorption
spectrum
spanning
from
UV
over
visible
up
near‐infrared
region
latter
an
ultra‐narrow
at
specific,
targeted
wavelength.
In
order
design
satisfying
demands,
fundamental
insights
relationship
provided
depending
molecular
packing
arrangement
resultant
coupling
thereof.
Based
recent
advancements
theoretical
understanding
intermolecular
between
slip‐stacked
dyes,
distinguishing
classical
J‐aggregates
with
predominant
long‐range
Coulomb
charge
transfer
(CT)‐mediated
or
‐coupled
J‐aggregates,
whose
red‐shifts
primarily
governed
by
short‐range
orbital
interactions,
is
suggested.
Within
this
framework,
aggregate
structure
functional
representative
classes
dye
aggregates
analyzed
most
advanced
OSCs
wavelength‐selective
OPDs,
providing
important
into
rational
thin‐film
materials.
Journal of the American Chemical Society,
Journal Year:
2021,
Volume and Issue:
143(50), P. 21143 - 21160
Published: Dec. 8, 2021
Fluorescent
organic
dyes
have
been
extensively
used
as
raw
materials
for
the
development
of
versatile
imaging
tools
in
field
biomedicine.
Particularly,
solid-state
fluorophores
(SSOFs)
past
20
years
has
exhibited
an
upward
trend.
In
recent
years,
studies
on
SSOFs
focused
advanced
tools,
such
optical
contrast
agents
and
phototherapy
agents,
biomedical
applications.
However,
practical
application
these
hindered
owing
to
several
limitations.
Thus,
this
Perspective,
we
provided
insights
that
could
aid
researchers
further
develop
overcome
limitations
limited
aqueous
dispersibility,
low
biocompatibility,
uncontrolled
emission.
First,
described
inherent
photophysical
properties
fluorescence
mechanisms
conventional,
aggregation-induced
emissive,
precipitating
with
respect
their
Subsequently,
highlighted
functionalized
bioimaging,
biosensing,
theranostics.
Finally,
elucidated
potential
prospects
current
SSOF-based
associated
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(33), P. 14976 - 14991
Published: July 29, 2022
The
creation
and
development
of
new
forms
nanocarbons
have
fundamentally
transformed
the
scientific
landscape
in
past
three
decades.
As
members
nanocarbon
family
with
accurate
size,
shape,
edge
structure,
molecular
carbon
imides
(MCIs)
shown
unexpected
unique
properties.
Particularly,
imide
functionalization
strategy
has
endowed
these
rylene-based
carbons
fascinating
characteristics
involving
flexible
syntheses,
tailor-made
structures,
diverse
properties,
excellent
processability,
good
stability.
This
Perspective
elaborates
design
evolution
to
functional
landscapes,
illustrative
examples
are
given,
including
a
promising
library
multi-size
multi-dimensional
MCIs
rigidly
conjugated
π-architectures,
ranging
from
1D
nanoribbon
2D
nanographene
cross-dimensional
MCIs.
Although
researchers
achieved
substantial
progress
using
as
components
for
exploration
charge
transport,
photoelectric
conversion,
chiral
luminescence
performances,
they
far
unleashing
their
full
potential.
Developing
highly
efficient
regioselective
coupling/ring-closure
reactions
formation
multiple
C–C
bonds
annulation
electron-deficient
aromatic
units
is
crucial.
Prediction
by
theory
help
machine
learning
artificial
intelligence
research
along
reliable
nanotechnology
characterization
will
give
an
impetus
blossom
related
fields.
Future
investigations
also
advance
toward─or
even
focus
on─the
emerging
potential
functions,
especially
fields
electronics
spin
electronics,
which
expected
open
avenues.
Nature Communications,
Journal Year:
2023,
Volume and Issue:
14(1)
Published: Jan. 25, 2023
Abstract
Nonconjugated
and
nonaromatic
luminophores
based
on
clustering-triggered
emission
derived
from
through-space
conjugation
have
drawn
emerging
attention
in
recent
years.
The
reported
nonconventional
are
emissive
concentrated
solution
and/or
the
solid
state,
but
they
tend
to
be
nonluminescent
dilute
solution,
which
greatly
limits
their
sensing
imaging
applications.
Herein,
we
design
unique
clusteroluminogens
through
modification
of
cyclodextrin
(CD)
with
amino
acids
enable
intermolecular
intramolecular
clusterization
chromophores
CD-based
confined
space.
resulted
interactions
along
conformation
rigidification
originated
hydrogen
bond
interaction
complexation
generate
blue
cyan
fluorescence
even
(0.035
wt.%,
quantum
yield
40.70%).
Moreover,
prepared
histidine-modified
CD
(CDHis)
is
demonstrated
for
fluorescent
detection
chlortetracycline
high
sensitivity
selectivity.
This
work
provides
a
new
universal
strategy
synthesize
bright
aqueous
molecular-level
enhanced
clusterization-triggered
emission.
Nature Communications,
Journal Year:
2023,
Volume and Issue:
14(1)
Published: April 3, 2023
Abstract
J-aggregation,
an
effective
strategy
to
extend
wavelength,
has
been
considered
as
a
promising
method
for
constructing
NIR-II
fluorophores.
However,
due
weak
intermolecular
interactions,
conventional
J-aggregates
are
easily
decomposed
into
monomers
in
the
biological
environment.
Although
adding
external
carriers
could
help
stabilize,
such
methods
still
suffer
from
high-concentration
dependence
and
unsuitable
activatable
probes
design.
Besides,
these
carriers-assisted
nanoparticles
risky
of
disassembly
lipophilic
Herein,
by
fusing
precipitated
dye
(HPQ)
which
orderly
self-assembly
structure,
onto
simple
hemi-cyanine
conjugated
system,
we
construct
series
activatable,
high-stability
NIR-II-J-aggregates
overcome
carrier’s
situ
vivo.
Further,
employ
probe
HPQ-Zzh-B
achieve
long-term
imaging
tumor
precise
resection
navigation
reducing
lung
metastasis.
We
believe
this
will
advance
development
controllable
bioimaging
Nature Communications,
Journal Year:
2023,
Volume and Issue:
14(1)
Published: April 6, 2023
Abstract
Perylene
bisimide
(PBI)
dyes
are
known
as
red,
maroon
and
black
pigments,
whose
colors
depend
on
the
close
π−π
stacking
arrangement.
However,
contrary
to
luminescent
monomers,
deep-red
PBI
pigments
commonly
non-
or
only
weakly
fluorescent
due
(multiple)
quenching
pathways.
Here,
we
introduce
N
-alkoxybenzyl
substituted
PBIs
that
contain
π
arrangement
(exhibiting
d
≈
3.5
Å,
longitudinal
transversal
displacements
of
3.1
Å
1.3
Å);
however,
they
afford
emitters
with
solid-state
fluorescence
quantum
yields
(
Φ
F
)
up
60%.
Systematic
photophysical
computational
studies
in
solution
solid
state
reveal
a
sensitive
interconversion
PBI-centred
locally
excited
charge
transfer
state,
which
depends
dihedral
angle
θ
between
benzyl
alkoxy
groups.
This
effectively
controls
emission
process,
enables
high
by
circumventing
common
pathways
observed
for
perylene
analogues.
The Journal of Physical Chemistry C,
Journal Year:
2024,
Volume and Issue:
128(1), P. 248 - 260
Published: Jan. 2, 2024
The
relationship
between
symmetry-breaking
charge
separation
(SB-CS)
and
null
aggregate
(NA)
formation
in
molecular
dimer
complexes
is
investigated
theoretically,
with
applications
mainly
to
dimers
based
on
PDI
chromophores.
Both
processes
derive
from
points,
which
are
defined
by
degeneracies
either
the
upper
or
lower
adiabatic
exciton
bands.
Hamiltonian
contains
intermolecular
coupling
derived
interacting
transition
dipole
moments
(Coulomb
coupling),
gives
rise
Frenkel
excitons,
as
well
excitons
charge-transfer
(CT)
driven
electron
(te)
hole
(th)
hopping
integrals.
A
recipe
for
efficient
SB-CS
presented,
which,
beyond
Weller
condition─which
holds
that
solvent-stabilized
CT
state
should
appear
below
optical
gap
-includes
two
additional
conditions:
presence
of
a
point
and,
just
important,
lopsided
transfer
integrals,
|te|
≫
|th|
|te|.
When
such
conditions
met,
developing
asymmetry
optimized
response
small
fluctuations
polar
solvent-induced
electric
field,
eventually
leads
charge-separated
state.
It
shown
can
also
occur
H-dimers
significant
cofacial
overlap,
consistent
observations
made
several
groups.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(27)
Published: March 31, 2022
Abstract
Chirality
is
a
particularly
important
concept
in
nature
and
exists
at
all
length
scales,
ranging
from
the
molecular
level
to
supramolecular
level.
Over
last
two
decades,
various
design
strategies
have
been
developed
construct
chiral
materials
based
on
perylene
diimides
(PDIs)
mimic
assembly
process
biological
systems,
but
applications
of
these
aggregates
are
still
an
early
stage.
This
Minireview
summarizes
recent
progress
synthesis
properties
PDIs.
The
chirality
PDI‐based
can
be
generated
by
three
different
approaches:
twisted
planes
PDIs,
substituents
co‐assembly
achiral
PDIs
guests.
A
comprehensive
understanding
as
well
potential
future
developments
also
provided.