The Journal of Physical Chemistry Letters,
Journal Year:
2024,
Volume and Issue:
15(51), P. 12561 - 12570
Published: Dec. 16, 2024
Intramolecular
singlet
fission
(SF)
in
multichromophore
systems
is
of
high
interest
for
photovoltaic
application.
As
an
attractive
candidate
SF-based
devices,
enabling
efficient
SF
covalent
oligomers
perylene
diimide
(PDI)
still
remains
challenging.
In
this
work,
inter-PDI
with
τSF
=
∼150
ps
and
∼150%
triplet
yield
a
tetramer
COTh-FPDI
was
facilitated
by
employing
saddle-shaped
cyclooctatetrathiophene
(COTh)
core
fused
linking
PDIs.
comparison,
ultrafast
symmetry-breaking
charge
separation
(τCS
∼100
fs)
observed
the
COTh-αPDI
flexible
linking.
Taking
advantage
rigid
minimized
excited-state
structural
relaxation,
unique
geometry
can
be
fully
defined
topological
characteristic
COTh,
which
plays
key
role
electronic
coupling
required
SF.
Our
work
provides
new
strategy
intramolecular
predefining
interchromophore
structure,
might
inspired
future
designing
systems.
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.
Inorganic Chemistry,
Journal Year:
2024,
Volume and Issue:
63(7), P. 3327 - 3334
Published: Feb. 5, 2024
Recently,
facilely
designable
metal–organic
frameworks
have
gained
attention
in
the
construction
of
photothermal
conversion
materials.
Nonetheless,
most
previously
reported
exhibit
limited
light
absorption
capabilities.
In
this
work,
a
distinctive
framework
with
heterogeneous
periodic
alternate
spatial
arrangements
metal–oxygen
clusters
and
perylene-based
derivative
molecules
was
prepared
by
situ
synthesis.
The
building
blocks
inimitable
structure
behave
as
both
electron
donors
acceptors,
giving
rise
to
significant
inherent
charge
transfer
crystalline
material,
resulting
narrow
band
gap
excellent
panchromatic
absorption,
ground
state
being
state.
Moreover,
it
can
retain
air-,
photo-,
water-stability
solid
stability
broad
characteristics
enable
effective
realization
near-infrared
(NIR)
conversion,
including
infrequent
NIR-II
framework.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(49)
Published: Oct. 5, 2023
Abstract
The
functionalization
of
π‐conjugated
scaffolds
with
sterically
demanding
substituents
is
a
widely
used
tactic
to
suppress
cofacial
(H‐type)
stacking
interactions,
which
may
even
inhibit
self‐assembly.
Contrary
expectations,
we
demonstrate
herein
that
increasing
steric
effects
can
result
in
an
enhanced
thermodynamic
stability
H‐type
supramolecular
polymers.
In
our
approach,
have
investigated
two
boron
dipyrromethene
(BODIPY)
dyes
bulky
phenyl
(
2
)
and
mesityl
3
meso
‐substituents
compared
their
self‐assembly
nonpolar
media
parent
‐methyl
BODIPY
1
lacking
groups.
While
the
demand
induces
pathway
complexity,
superior
pathways
be
rationalized
terms
additional
enthalpic
gain
arising
from
intermolecular
C−H⋅⋅⋅F−B
interactions
orthogonally
arranged
aromatic
substituents,
overrule
inherent
demand.
Our
findings
underline
importance
balancing
competing
non‐covalent
Materials Advances,
Journal Year:
2023,
Volume and Issue:
5(3), P. 1056 - 1064
Published: Nov. 23, 2023
A
crystal
engineering
approach
has
been
used
to
investigate
the
integrated
impact
of
functionalization
and
co-crystallization
on
photophysical
properties
organic
solids.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Sept. 12, 2024
The
properties
and
functions
of
chromophores
utilized
by
nature
are
strongly
affected
the
environment
formed
protein
structure
in
cells
surrounding
them.
This
concept
is
transferred
here
to
host-guest
complexes
with
encapsulated
guests
acting
as
an
environmental
stimulus.
A
new
cyclophane
host
based
on
coronene
bisimide
presented
that
can
encapsulate
a
wide
variety
planar
guest
molecules
binding
constants
up
(4.29
±
0.32)
×
10
Nature Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 14, 2025
Abstract
The
mechanistic
understanding
of
light-driven
charge
separation
and
charge-carrier
transport
within
the
frameworks
π-conjugated
molecules
is
imperative
to
mimic
natural
photosynthesis
derive
synthetic
materials
for
solar
energy
conversion.
In
this
regard,
since
late
1980s,
distance
solvent
dependence
stepwise
(incoherent)
hopping
versus
single-step
(coherent)
superexchange
(tunnelling)
have
been
studied
in
detail.
Here
we
introduce
structurally
highly
defined
cofacially
stacked
donor–acceptor
perylene
bisimide
arrays,
which
offer
a
high
resemblance
systems.
Similarity
achieved
through
controlling
electron
transfer
processes
via
intermolecular
interactions
between
π-stacked
subunits.
Selective
excitation
donor
induces
acceptor
unit
polar
solvents,
facilitated
by
‘through-stack’
wire-like
mechanism
with
low
attenuation
factor
β
=
0.21
Å
−1
,
suggests
through-stack
as
being
equally
supportive
long-distance
sequential
compared
investigated
‘through-bond’
along
bridges.
The Journal of Physical Chemistry B,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 25, 2025
Understanding
the
interplay
between
excimer
formation
and
symmetry-breaking
charge
separation
is
important
for
optimizing
in
organic
photovoltaic
materials.
To
explore
this
connection,
we
synthesized
four
1,6,7,12-tetrakis(p-X-phenoxy)perylene-(3,4:9,10)-bisdicarboximide
cofacially
stacked
dimers,
where
X
=
MeO,
tert-butyl,
Br,
CF3.
Steady-state
spectroscopy
reveals
H-type
aggregation
all
while
transient
absorption
shows
relatively
small
changes
their
excited-state
absorptions.
However,
time-resolved
fluorescence
(TRF)
that
relaxation
occurs
from
an
initial
Frenkel
exciton-dominated
state
to
one
which
transfer
(CT)
character
contributes.
Relaxation
lower-lying
with
CT
attributed
a
combination
of
structural
distribution
elicited
by
varying
substituents.
This
study
illustrates
how
subtle
structure
can
combine
influence
excited
dynamics
molecular
dimers.
The Journal of Physical Chemistry B,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Sept. 5, 2024
The
impact
of
conformational
change
on
the
ground
and
excited
states
seven
perylene
diimide
(PDI)-based
dimeric
systems
is
examined
by
introducing
longitudinal
shift,
transverse
rotation
one
monomer
with
respect
to
another.
minimum
energy
conformations
are
compared
via
an
decomposition
analysis.
heteroatom-substituted
systems,
such
as
B
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Aug. 2, 2024
Perylene
diimide
(PDI)
dimers
and
higher
aggregates
are
key
components
in
organic
molecular
photonics
photovoltaic
devices,
supporting
singlet
fission
symmetry
breaking
charge
separation.
Detailed
understanding
of
their
excited
states
is
thus
important.
This
has
proven
challenging
because
interchromophoric
coupling
a
strong
function
dimer
architecture.
Recently,
macrocyclic
PDI
was
reported
which
excitonic
could
be
turned
on
off
simply
by
changing
the
solvent.
presents
useful
case
where
modified
without
synthetic
changes
to
tune
supramolecular
structure.
Here
we
present
detailed
study
solvent
dependent
state
dynamics
this
means
coherent
multidimensional
spectroscopy.
Spectral
analysis
resolves
different
strengths,
consistent
with
conformation.
The
strongly
coupled
conformer
forms
an
excimer
within
300
fs.
low-frequency
Raman
active
modes
recovered
from
two-dimensional
electronic
spectra
reveal
frequencies
characteristic
exciton
coupling.
These
assigned
modulating
corresponding
DFT
calculations.
Further
reveals
time
frequency
during
formation.
Analysis
"beatmaps"
features
not
predicted
displaced
harmonic
oscillator
model
vibronic
