Cell Reports Physical Science,
Год журнала:
2024,
Номер
5(7), С. 102045 - 102045
Опубликована: Июнь 13, 2024
Molecular
dimers
are
generally
regarded
as
essential
tools
for
probing
structure-property
relationships
in
condensed-phase
systems,
revealing
complexities
where
structural
tuning
is
challenging.
Traditionally
treated
"static,"
with
properties
defined
by
their
optimized
geometry,
we
argue
that
"dynamic,"
exhibiting
considerable
conformational
heterogeneity
over
time,
which
significantly
influences
interchromophore
coupling
strengths.
Illustrating
this,
explore
the
singlet
fission
dynamics
of
a
pentacene
dimer
linked
phenyl-diketopyrrolopyrrole
and
acetylene
bridges.
The
unrestricted
rotations
yield
myriad
rotational
conformers,
each
altering
processes,
evident
through
excitation-energy-dependent
transient
absorption
electron
paramagnetic
resonance
spectroscopy.
This
necessitates
considering
not
only
broad
distribution
rate
constants
but
also
multidimensional
potential-energy
surfaces
multiple
sub-ensembles,
leading
to
"heterogeneous
fission."
Consequently,
these
findings
challenge
prevailing
static
approach
molecular
photophysics,
suggesting
individual
steps
excited-state
relaxation
pathways
cannot
be
delineated
unique
yields.
Chemical Reviews,
Год журнала:
2023,
Номер
123(18), С. 10877 - 10919
Опубликована: Сен. 8, 2023
The
interaction
between
molecular
electronic
transitions
and
electromagnetic
fields
can
be
enlarged
to
the
point
where
distinct
hybrid
light-matter
states,
polaritons,
emerge.
photonic
contribution
these
states
results
in
increased
complexity
as
well
an
opening
modify
photophysics
photochemistry
beyond
what
normally
seen
organic
molecules.
It
is
today
evident
that
polaritons
offer
opportunities
for
photophysics,
which
has
caused
ever-rising
interest
field.
Focusing
on
experimental
landmarks,
this
review
takes
its
reader
from
advent
of
field
polaritonic
chemistry,
over
split
into
polariton
chemistry
photochemistry,
present
day
status
within
photophysics.
To
introduce
field,
starts
with
a
general
description
interactions,
how
enhance
these,
characterizes
coupling
strength.
Then
strongly
coupled
systems
using
Fabry-Perot
plasmonic
cavities
are
described.
This
followed
by
room-temperature
Bose-Einstein
condensation/polariton
lasing
systems.
ends
discussion
benefits,
limitations,
future
developments
strong
exciton-photon
Chemical Reviews,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 12, 2024
Since
the
seminal
report
by
Adachi
and
co-workers
in
2012,
there
has
been
a
veritable
explosion
of
interest
design
thermally
activated
delayed
fluorescence
(TADF)
compounds,
particularly
as
emitters
for
organic
light-emitting
diodes
(OLEDs).
With
rapid
advancements
innovation
materials
design,
efficiencies
TADF
OLEDs
each
primary
color
points
well
white
devices
now
rival
those
state-of-the-art
phosphorescent
emitters.
Beyond
electroluminescent
devices,
compounds
have
also
found
increasing
utility
applications
numerous
related
fields,
from
photocatalysis,
to
sensing,
imaging
beyond.
Following
our
previous
review
2017
(
ACS Central Science,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 21, 2025
Triplet-triplet
annihilation
photon
upconversion
(TTA-UC)
systems
hold
great
promise
for
applications
in
energy,
3D
printing,
and
photopharmacology.
However,
their
optimization
remains
challenging
due
to
the
need
precise
tuning
of
sensitizer
annihilator
concentrations
under
oxygen-free
conditions.
This
study
presents
an
automated,
high-throughput
platform
discovery
TTA-UC
systems.
Capable
performing
100
concentration
scans
just
two
hours,
generates
comprehensive
maps
critical
parameters,
including
quantum
yield,
triplet
energy
transfer
efficiency,
threshold
intensity.
Using
this
approach,
we
identify
key
loss
mechanisms
both
established
novel
At
high
porphyrin-based
concentrations,
yield
losses
are
attributed
self-quenching
via
aggregation
triplet-triplet
(sensitizer-TTA).
Additionally,
reverse
(RTET)
at
elevated
levels
increases
excitation
thresholds.
Testing
sensitizer-annihilator
pairs
confirms
these
mechanisms,
highlighting
opportunities
molecular
design
improvements.
automated
offers
a
powerful
tool
advancing
research
other
photochemical
studies
requiring
low
oxygen
levels,
intense
laser
excitation,
minimal
material
use.
Near-infrared
(NIR)
to
blue
triplet-triplet
annihilation
upconversion
(TTA-UC)
shows
unique
applications
in
optogenetics,
photocaging,
and
stereoscopic
three-dimensional
printing,
etc.
Here,
we
disclose
a
strategy
that
narrowed
the
energy
gap
between
triplet
states
of
NIR
photosensitizer
annihilator,
with
aim
maximally
suppressing
photoexcitation
loss
during
TET.
Hence,
produced
NIR-to-blue
TTA-UC
pair
exhibited
an
exceptionally
large
anti-Stokes
shift
(0.76
eV)
achieved
record
quantum
yield
(15.5%,
out
50%).
We
further
prepared
for
first
time
small,
water-dispersed,
oxygen-resistant
nanoparticles
up
1.8%.
Such
upconverted
were
successfully
utilized
as
NIR-responsive
photocatalysts
reversible
transformation
enzyme
cofactor
NAD+/NADH
photobiocatalytic
system
air-saturated
aqueous
solutions.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(20), С. 11402 - 11414
Опубликована: Май 15, 2023
Sensitized
triplet–triplet
annihilation
upconversion
is
a
promising
strategy
to
use
visible
light
for
chemical
reactions
requiring
the
energy
input
of
UV
photons.
This
avoids
unsafe
ultraviolet
sources
and
can
mitigate
photo-damage
provide
access
reactions,
which
filter
effects
hamper
direct
excitation.
Here,
we
report
new
approach
make
blue-to-UV
more
amenable
photochemical
applications.
The
tethering
naphthalene
unit
cyclometalated
iridium(III)
complex
yields
bichromophore
with
high
triplet
(2.68
eV)
naphthalene-based
reservoir
featuring
lifetime
72.1
μs,
roughly
factor
20
longer
than
photoactive
excited
state
parent
complex.
In
combination
three
different
annihilators,
consistently
lower
thresholds
crossover
from
quadratic
into
linear
excitation
power
dependence
regime
were
observed
compared
system
composed
2,5-diphenyloxazole
annihilator
sufficiently
robust
under
long-term
blue
irradiation
continuously
high-energy
singlet-excited
that
drive
normally
light.
Both
photoredox
transfer
catalyses
feasible
using
this
concept,
including
reductive
N–O
bond
cleavage
Weinreb
amides,
C–C
coupling
reaction
based
on
aryl
debromination,
two
Paternò–Büchi
[2
+
2]
cycloaddition
reactions.
Our
work
seems
relevant
in
context
developing
strategies
driving
energetically
demanding
photochemistry
low-energy
