Chinese Journal of Chemistry,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Dec. 13, 2024
Comprehensive
Summary
A
design
strategy
towards
stable
fluorenyl
radicals
(
FR
s)
has
been
developed
through
introducing
donor‐π‐radical
(D‐π‐R)
conjugation,
facilitated
by
the
linkage
of
amine
N
atoms
and
centers
via
phenyl
or
9‐anthryl
moieties.
Four
s,
with
without
atom
containing
protecting
groups,
were
designed
synthesized
for
comparative
analysis.
X‐ray
crystallographic
studies
revealed
planar
skeletons
CDP‐FR
MA‐FR
,
which
exhibit
significant
dihedral
angles
relative
to
their
groups.
Wiberg
bond‐order
analysis
natural
bond
orbital
conducted
on
C‐C
C‐N
between
radical
center
in
all
s
clearly
demonstrated
presence
D‐π‐R
conjugation.
Furthermore,
time‐dependent
DFT
calculations,
based
frontier
molecular
analysis,
highlighted
contribution
structures
as
donor‐acceptor
effect
lowest
energy
absorptions
carbazole
diphenylamine
substituted
DPAA‐FR
would
promote
charge
transfer
process
inhibit
photodegradation
reaction.
Consequently,
beneficial
from
conjugations,
exhibited
superior
photostability
compared
TP‐FR
.
Our
study
offers
a
new
synthesis
persistent
monoradicals.
Nature Photonics,
Journal Year:
2024,
Volume and Issue:
18(9), P. 905 - 912
Published: June 19, 2024
Abstract
The
development
of
luminescent
organic
radicals
has
resulted
in
materials
with
excellent
optical
properties
for
near-infrared
emission.
Applications
light
generation
this
range
span
from
bioimaging
to
surveillance.
Although
the
unpaired
electron
arrangements
enable
efficient
radiative
transitions
within
doublet-spin
manifold
light-emitting
diodes,
their
performance
is
limited
by
non-radiative
pathways
introduced
electroluminescence.
Here
we
present
a
host–guest
design
diodes
that
exploits
energy
transfer
up
9.6%
external
quantum
efficiency
800
nm
tris(2,4,6-trichlorophenyl)methyl-triphenyl-amine
radical
guest
energy-matched
triplet
state
charge-transporting
anthracene-derivative
host.
We
show
spectroscopy
and
quantum-chemical
modelling
reversible
triplet–doublet
allows
harvesting
host
excitons.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Sept. 2, 2024
Purely
organic
molecules
exhibiting
near-infrared
(NIR)
emission
possess
considerable
potential
for
applications
in
both
biological
and
optoelectronic
technological
domains,
owing
to
their
inherent
advantages
such
as
cost-effectiveness,
biocompatibility,
facile
chemical
modifiability.
However,
the
repertoire
of
with
peaks
exceeding
750
nm
concurrently
demonstrating
high
photoluminescence
quantum
efficiency
(PLQE)
remains
relatively
scarce
due
energy
gap
law.
Herein,
we
report
two
open-shell
NIR
radical
emitters,
denoted
DMNA-Cz-BTM
DMNA-PyID-BTM,
achieved
through
strategic
integration
a
donor
group
(DMNA)
onto
Cz-BTM
PyID-BTM
frameworks,
respectively.
We
found
that
donor-acceptor
molecular
structure
allows
designed
emitters
exhibit
charge-transfer
excited
state
spatially
separated
electron
hole
levels
non-bonding
characteristics.
Thus,
high-frequency
vibrations
are
effectively
suppressed.
Besides,
reduction
low-frequency
is
observed.
Collectively,
non-radiative
decay
channel
significantly
suppressed,
leading
exceptional
PLQE
values.
Specifically,
manifests
an
peak
at
758
alongside
55
%,
whereas
DMNA-PyID-BTM
exhibits
778
66
%.
Notably,
these
represent
pinnacle
among
metal-free
surpassing
nm.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Nov. 11, 2024
The
development
of
novel
ladder-type
conjugated
molecules
is
crucial
for
advancing
supramolecular
chemistry
and
material
science.
In
this
study,
we
report
a
straightforward
synthesis
new
alternating
donor-acceptor
(D-A)
heteroarene,
FCDTDPP,
demonstrate
its
application
as
photothermal
agent
imaging
cancer
therapy.
FCDTDPP
constructed
by
vinylene
bridge
between
cyclopentadithiophene
(D)
diketopyrrolopyrrole
(A)
through
intramolecular
Friedel-Crafts
type
reaction.
exhibits
unique
combination
good
molecular
planarity,
efficient
intra-/intermolecular
mixed
D-A
interactions,
local
aromaticity.
These
features
collectively
contribute
to
broad
intense
absorptions
with
narrow
band
gap
in
red
the
spectra,
coupled
multiple
vibrational
absorption
feature,
thereby
enhancing
non-radiative
decay
process
resulting
conversion
property.
nanoparticles
(NPs)
exhibit
superior
performance
stability
under
660
nm
laser
irradiation.
Moreover,
vitro
studies
reveal
that
NPs
possess
excellent
biocompatibility,
low
cytotoxicity,
robust
therapeutic
efficacy,
finding
further
corroborated
preliminary
vivo
experiments
tumor-bearing
mice.
This
work
charts
course
engineering
organic
systems,
propelling
relevant
research
forward.
ACS Central Science,
Journal Year:
2025,
Volume and Issue:
11(1), P. 116 - 126
Published: Jan. 3, 2025
In
quantum
information
science
and
sensing,
electron
spins
are
often
purified
into
a
specific
polarization
through
an
optical-spin
interface,
process
known
as
optically
detected
magnetic
resonance
(ODMR).
Diamond-NV
centers
transition
metals
both
excellent
platforms
for
these
so-called
color
centers,
while
metal-free
molecular
analogues
also
gaining
popularity
their
extended
lifetimes,
milder
environmental
impacts,
reduced
costs.
our
earlier
attempt
at
designing
such
organic
high-spin
π-diradicals,
we
proposed
to
spin-polarize
by
shelving
triplet
MS
=
±1
populations
singlets.
This
was
recently
verified
experiments
albeit
with
low
ODMR
contrasts
of
<1%
temperatures
above
5
K.
this
work,
propose
improve
the
signal
moving
singlet
back
0
sublevel,
true
carbon-based
analogue
NV
center.
Our
proposal
is
based
upon
transition-orbital
group-theoretical
analyses
beyond-nearest-neighbor
spin–orbit
couplings,
which
further
confirmed
ab
initio
calculations
realistic
trityl-based
radical
dimer.
Microkinetic
point
toward
high
around
30%
under
experimentally
feasible
conditions,
stark
improvement
from
previous
works.
Finally,
in
quest
ground-state
addressable
spin
qubits,
exemplify
how
symmetry-based
design
avoids
Zeeman-induced
singlet–triplet
mixings,
setting
scene
realizing
qubit
gates.
The Journal of Physical Chemistry C,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 10, 2025
We
report
a
nonadiabatic
molecular
dynamics
(NA-MD)
study
on
radiative
and
nonradiative
recombination
in
small
bare
hydrated
titania
nanoclusters,
(TiO2)4(H2O)m
(m
=
0,
2,
4)
(TiO2)8(H2O)m
5).
Our
findings
indicate
that
increased
hydration
raises
excitation
energies
couplings,
accelerating
both
recombination.
test
the
robustness
of
this
predicted
trend
with
respect
to
several
important
choices
our
NA-MD
methodology.
find
nuclear
trajectories
from
classical
force
fields
closely
match
those
density
functional
theory
(DFT)
calculations,
time
scales
weakly
dependent
choice
pure
or
hybrid
functionals.
Additionally,
decoherence
corrections
yield
longer
times
than
overcoherent
fewest
switches
algorithm.
Overall,
hydration-induced
acceleration
nanoclusters
is
found
be
independent
main
approach,
thus
giving
us
confidence
results.
Nature Communications,
Journal Year:
2025,
Volume and Issue:
16(1)
Published: Feb. 3, 2025
Aromatic
belts,
ultrashort
carbon
nanotubes,
and
related
structures,
are
emerging
molecular
entities
in
the
fields
of
organic
electronics
supramolecular
chemistry
owing
to
their
structural
rigidity,
fully
fused
π-conjugation,
well-defined
cavity.
Synthesis
aromatic
belts
with
embedded
thiophene
which
manifest
significant
optoelectronic
conductive
properties,
has
not
yet
been
achieved.
Herein,
we
report
synthesis
thiophene-fused
(thiophene
belts)
via
one-step
sulfur
cross-linking
reaction
partially
fluorinated
cycloparaphenylenes.
Their
features,
including
unidirectional
columnar
stacking
high
dipole
moment
crystals,
two-dimensional
layer
assembly
on
metal
surfaces,
photophysical
such
as
long-lifetime
phosphorescence,
uncovered.
These
distinctive
features
should
inspire
a
range
applications
devices
polar
materials.
authors
The Journal of Chemical Physics,
Journal Year:
2025,
Volume and Issue:
162(6)
Published: Feb. 10, 2025
Light-emitting
molecules
have
been
extensively
studied
due
to
their
potential
and
wide
variety
of
applications
from
optoelectronic
devices
biomedical
applications.
To
fully
understand
rationalize
the
light-emitting
process
for
innovation
next-generation
applications,
it
is
vital
reveal
dynamic
behavior
excitons,
where
excited
electronic
states
(locally
excited,
charge
transfer,
separated
states),
spin
multiplicity,
motion
atomic
nucleus
are
interacting
each
other.
Here,
we
will
show
our
recent
progress
on
systems
developed
under
“Dynamic
Exciton”
project
in
Japan.
Applied Physics Letters,
Journal Year:
2025,
Volume and Issue:
126(10)
Published: March 1, 2025
The
doublet
emission
from
organic
open-shell
monoradicals
is
spin-allowed,
enabling
100%
internal
quantum
efficiency
when
electroexcitation
occurs
in
light-emitting
diodes.
Research
works
on
luminescent
radicals
have
shown
significant
potential
for
high-efficiency
electroluminescence,
achieving
device
efficiencies
comparable
to
those
of
close-shell
emitters.
This
Perspective
reviews
recent
advancements
spin-doublet
monoradicals,
highlighting
molecular
design
principles,
optimizations,
and
futures.
