The Journal of Physical Chemistry Letters,
Год журнала:
2024,
Номер
15(46), С. 11657 - 11663
Опубликована: Ноя. 14, 2024
The
thermally
activated
delayed
fluorescence
(TADF)
originating
from
high-level
intersystem
crossing
(hRISC)
presents
great
potential
in
realizing
a
more
full
utilization
of
triplet
excitons.
In
this
study,
DPA-FBP
and
TPA-FBP
were
doped
PMMA
film
with
different
weight
fractions
to
study
the
effect
aggregation
on
luminescence
properties.
As
result,
TADF
feature
hRISC
was
only
found
50
wt
%
film,
whereas
1
shows
prompt
fluorescence.
fs-TA
spectroscopy
results
reveal
that
will
generate
charge
transfer
species
lower
energy
gap,
so
high-lying
exciton
can
transition
back
singlet
state,
quickly
lowest
state
due
unfavorable
splitting.
This
provides
new
insight
into
effects
excited-state
properties
hot
materials
solid-state
photodynamic.
Advanced Functional Materials,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 2, 2025
Abstract
Near‐infrared
(NIR)
light‐driven
photocatalysis
provides
a
promising
solution
to
the
inherent
limitations
of
conventional
ultraviolet
(UV)
and
visible‐light
photocatalysis,
such
as
shallow
penetration,
photodamage
from
high‐energy
irradiation,
limited
selectivity.
However,
effective
strategies
for
achieving
NIR
remain
scarce.
Here,
novel
strategy
that
achieves
with
significantly
enhanced
selectivity
is
reported
through
lanthanide
nanocrystal‐mediated
photosensitization.
A
composite
nanocatalyst,
comprising
NaNdF
4
nanocrystals
Zn(II)
phthalocyanine
organic
photosensitizers
designed,
where
absorb
808
nm
light
transfer
energy
directly
via
lanthanide‐mediated
triplet
sensitization.
This
approach
enables
selective
functionalization
substrates
increased
yields
reduced
side‐product
formation
compared
UV/visible
excitation.
The
arises
controlled
generation
superoxide
anions
(O
2
−
)
reactive
oxygen
species
(ROS)
minimized
substrate
photoactivation.
targeted
dehydrogenation
C─N
coupling
reactions
diverse
N‐heterocyclic
substrates,
including
halogen‐substituted
compounds
are
typically
prone
undesired
side
reactions.
findings
establish
versatile
improving
in
photocatalytic
transformations,
opening
new
opportunities
light‐sensitive
synthesis
sustainable
catalysis.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
unknown
Опубликована: Сен. 19, 2024
Copper
nanoclusters
(Cu
NCs)
characterized
by
their
well-defined
electronic
and
optical
properties
are
an
ideal
platform
for
organic
photocatalysis
exploring
atomic-level
behaviors.
However,
potential
as
greener,
efficient
catalysts
challenging
reactions
like
decarboxylative
oxygenation
under
mild
conditions
remains
unexplored.
Herein,
we
present
Cu
ACS Catalysis,
Год журнала:
2024,
Номер
14(16), С. 11974 - 11989
Опубликована: Июль 26, 2024
Photoactive
copper
complexes
have
gained
significant
attention
due
to
their
photocatalytic
activities.
Different
homogeneous
Cu(I)
complexes,
Cu(II)
and
heterogeneous
copper-based
photocatalysts
been
investigated
utilized
in
a
broad
spectrum
of
organic
transformations.
These
applications
span
radical
additions,
C–C
bond
C–heteroatom
cross-couplings,
aerobic
oxidative
reactions,
kinetic
resolutions.
This
review
summarizes
the
advancements
this
dynamic
field
visible-light-induced,
excited-state
copper-catalyzed
reactions
over
recent
years.
It
is
organized
according
type
excited
species
involved
provides
perspective
on
current
future
developments.
For
the
majority
of
gold
nanoclusters
(NCs),
their
water
insolubility,
low
photoluminescence
(PL)
intensity,
and
less
understood
photostability
are
three
critical
factors
that
limit
application
in
biomedical
photocatalysis
fields.
In
this
study,
we
report
a
polymer
wrapping
method
for
phase
transfer
organic
soluble
NCs
into
aqueous
without
degrading
electronic
optical
properties,
such
materials
further
demonstrated
robust
water.
We
first
synthesized
Au18(DMBT)14
NC
(DMBT
=
2,4-dimethylbenzenethiolate)
found
aromatic
ligands
confer
greatly
enhanced
antioxidation
capability
compared
to
Au18(CHT)14
counterpart
(CHT
cyclohexanethiolate),
with
role
ligand
interactions
identified
by
X-ray
crystallography.
The
was
successfully
transferred
an
amphiphilic
(Pluronic
F127,
abbrev.
F127)
method,
producing
Au18-D@F127
nanoparticles
[each
containing
few
NCs;
Au18-D
is
abbreviation
Au18(DMBT)14]
10-fold
enhancement
PL
similar
results
were
also
obtained
Au18(CHT)14.
This
broadly
applicable
various
NCs,
rendering
solubility
significantly
enhancing
intensity
otherwise
weakly
emissive
NCs.
exceptional
stability
enables
NPs
photocatalytic
activation
persulfate
ions
subsequent
photodegradation
pollutants
efficiently.
Nature Communications,
Год журнала:
2025,
Номер
16(1)
Опубликована: Март 7, 2025
Abstract
The
modulation
of
traps
has
found
attractive
attention
to
optimize
the
performance
luminescent
materials,
while
understanding
trap-involved
photoluminescence
management
metal
nanoclusters
greatly
lags
behind,
thus
extensively
impeding
their
increasing
acceptance
as
promising
chromophores.
Here,
we
report
an
efficient
passivation
structural
oxygen
vacancies
in
AuAg
by
leveraging
H
2
O
molecules,
achieving
a
sensitive
color
tuning
from
536
480
nm
and
remarkably
boosting
quantum
yield
5.3%
(trap-state
emission)
91.6%
(native-state
emission).
In
detail,
favored
electron
transfer
relevant
contributes
weak
trap-state
emission,
which
is
capable
being
restrained
molecules
taking
Au-O
Ag-O
bonds.
This
scenario
allows
dominated
native-state
emission
with
faster
radiative
rate.
parallel,
can
rigidify
landscape
on
hydrogen
bonding,
enabling
suppression
electron-optical
phonon
coupling
decelerated
non-radiative
presented
study
deepens
tailoring
properties
manipulating
surface
trap
chemistry
relaxation
dynamics,
would
shed
new
light
customizable
performance.
Abstract
Precise
alloying
at
the
preferred
location
to
enhance
optical
properties
of
metal
nanoclusters
is
challenging
as
often
most
stable
isomer
produced.
To
alter
Au
atoms
on
[Au
12
Ag
32
(SR)
30
]
4−
cluster,
a
new
approach
by
changing
reacting
precursor
following
an
inter‐cluster
reaction
reported.
A
Au(I)
containing
18
Se
8
(DPPE)
6
2+
source,
while
with
[Ag
44
,
used,
and
occupy
surface
position
instead
core.
The
whole
monitored
in‐line
using
high‐resolution
trapped
ion
mobility
spectrometry
(TIMS),
change
in
collision
cross
section
(CCS)
intermediates
final
product
reveal
that
can
dynamically
migrate
within
cluster
all
out
.
Changing
shows
impact
NIR
II
emission
≈1340
nm
parent
synthesized
alloy
enhanced
tenfold
compared
≈20
blueshifted.
Density
functional
theory
calculations
Au/Ag
staple
are
slightly
positively
charged,
making
it
convenient
for
be
exchanged
surface.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 25, 2024
Abstract
Despite
recent
advances
in
cluster‐based
catalysis
for
organic
synthesis,
the
substrate
scope
of
reactions
catalyzed
by
metal
nanoclusters
is
typically
not
superior
to
previously
established
catalytic
systems.
Herein,
we
develop
new
atomically
precise
copper
protosilylation,
with
expanding
alkenes
and
simple
enynes
that
were
suitable
prior
synthetic
methodologies
traditional
complexes.
The
involvement
a
second
center
kernel
during
migratory
insertion
step
thought
be
responsible
expanded
scope.
In
addition,
reaction
highly
compatible
water
can
carried
out
open
air
rather
than
under
inert
gas
protection.
Mechanistic
studies
suggest
cluster‐catalyzed
protosilylation
proceeds
absence
silyl
radicals.
current
findings
demonstrate
potential
using
practical
sustainable
chemical
synthesis.
Angewandte Chemie,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 25, 2024
Abstract
Despite
recent
advances
in
cluster‐based
catalysis
for
organic
synthesis,
the
substrate
scope
of
reactions
catalyzed
by
metal
nanoclusters
is
typically
not
superior
to
previously
established
catalytic
systems.
Herein,
we
develop
new
atomically
precise
copper
protosilylation,
with
expanding
alkenes
and
simple
enynes
that
were
suitable
prior
synthetic
methodologies
traditional
complexes.
The
involvement
a
second
center
kernel
during
migratory
insertion
step
thought
be
responsible
expanded
scope.
In
addition,
reaction
highly
compatible
water
can
carried
out
open
air
rather
than
under
inert
gas
protection.
Mechanistic
studies
suggest
cluster‐catalyzed
protosilylation
proceeds
absence
silyl
radicals.
current
findings
demonstrate
potential
using
practical
sustainable
chemical
synthesis.
