Abstract
Donor‒acceptor
covalent
organic
frameworks
(D‒A
COFs)
have
been
regarded
as
promising
materials
for
photocatalytic
water
splitting
because
of
their
tunable
band
gaps.
However,
efficiency
is
hindered
by
fast
charge
recombination
and
low
photostability.
Herein,
we
proposed
a
donor
structural
engineering
strategy
improving
the
activity
D‒A
COFs
to
tackle
these
problems.
Two
benzothiadiazole‐based
(DHU‐COF‐BB
DHU‐COF‐BP)
with
distinct
donors
were
prepared
H
2
evolution
reaction
(HER).
As
comparison,
DHU‐COF‐TB
without
benzothiadiazole
moieties
was
also
designed
synthesized.
Impressively,
production
rate
DHU‐COF‐BB
reaches
12.80
mmol
g
−1
h
under
visible
light
irradiation
(≥420
nm),
which
nearly
2.0
3.1
times
higher
than
that
DHU‐COF‐BP
(6.47
)
(4.06
),
respectively.
In
addition,
apparent
quantum
(AQE)
up
5.04%
at
420
nm.
Photocatalytic
electrochemical
measurements
indicate
enhanced
hydrogen
can
be
ascribed
introduction
appropriate
benzene
moiety
into
donors,
increases
separation
thereby
suppresses
electron‒hole
recombination.
Density
functional
theory
(DFT)
calculations
revealed
both
triphenylamine
units
are
main
active
sites
HER
over
DHU‐COF‐BB.
This
work
provides
new
insight
strategy.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(24), С. 16609 - 16618
Опубликована: Июнь 5, 2024
Covalent
organic
frameworks
(COFs)
have
been
explored
for
photodynamic
therapy
(PDT)
of
cancer,
but
their
antitumor
efficacy
is
limited
by
excited
state
quenching
and
low
reactive
oxygen
species
generation
efficiency.
Herein,
we
report
a
simultaneous
protonation
metalation
strategy
to
significantly
enhance
the
PDT
nanoscale
two-dimensional
imine-linked
porphyrin-COF.
The
neutral
unmetalated
porphyrin-COF
(Ptp)
protonated
metalated
(Ptp-Fe)
were
synthesized
via
imine
condensation
between
5,10,15,20-tetrakis(4-aminophenyl)porphyrin
terephthalaldehyde
in
absence
presence
ferric
chloride,
respectively.
chloride
generated
both
doubly
Fe3+-coordinated
porphyrin
units,
which
red-shifted
increased
Q-band
absorption
disrupted
exciton
migration
prevent
quenching,
Under
light
irradiation,
rapid
energy
transfer
from
porphyrins
Ptp-Fe
enabled
1O2
hydroxyl
radical
type
II
I
processes.
also
catalyzed
conversion
hydrogen
peroxide
hydroxy
through
photoenhanced
Fenton-like
reaction
under
slightly
acidic
conditions
illumination.
As
result,
Ptp-Fe-mediated
exhibited
much
higher
cytotoxicity
than
Ptp-mediated
on
CT26
4T1
cancer
cells.
afforded
potent
subcutaneous
murine
colon
orthotopic
triple-negative
breast
tumors
prevented
metastasis
lungs.
This
work
underscores
role
fine-tuning
molecular
structures
COFs
enhancing
efficacy.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 2, 2025
Furthering
the
field
of
synthetic
organic
chemistry
from
discrete
molecules
regime
to
extended
structure
regime,
covalent
frameworks
(COFs)
represent
a
new
genre
crystalline
porous
materials
featuring
designability
with
molecular-level
precision,
well-defined
porosity,
and
exceptional
stability
imparted
by
robust
linkages
reticulating
molecules.
The
topology
COFs
is
principal
feature
that
regulates
their
functionality
usability
for
emerging
technologies.
Profound
comprehension
network
topologies
maneuvering
them
toward
targeted
applications
are
crucial
advancing
realm
COF
research
developing
novel
functional
exciting
breakthroughs.
In
this
Perspective,
we
discuss
recent
pursuits
contributing
discovery
highly
connected
nets
having
topologies,
assess
key
challenges
achieving
such
offer
insights
into
current
scenario
future
directions.
Molecules,
Год журнала:
2025,
Номер
30(4), С. 884 - 884
Опубликована: Фев. 14, 2025
Researchers
have
extensively
investigated
photosensitizer
(PS)
derivatives
for
various
applications
due
to
their
superior
photophysical
and
electrochemical
properties.
However,
inherent
problems,
such
as
instability
self-quenching
under
physiological
conditions,
limit
biological
applications.
Metal-organic
frameworks
(MOFs)
covalent
organic
(COFs)
represent
two
relatively
new
material
types.
These
materials
high
surface
areas
permanent
porosity,
they
show
a
tremendous
deal
of
potential
like
these.
This
review
summarizes
key
synthesis
processes
highlights
recent
advancements
in
integrating
PS-based
COF
MOF
nanocarriers
biomedical
while
addressing
obstacles
prospects.
Advanced Science,
Год журнала:
2024,
Номер
unknown
Опубликована: Июль 16, 2024
The
combination
of
cuproptosis
and
immune
checkpoint
inhibition
has
shown
promise
in
treating
malignant
tumors.
However,
it
remains
a
challenge
to
deliver
copper
ions
inhibitors
efficiently
simultaneously
Herein,
mitochondria-targeted
nanoscale
coordination
polymer
particle,
Cu/TI,
comprising
Cu(II),
triphenylphosphonium
conjugate
5-carboxy-8-hydroxyquinoline
(TI),
for
effective
induction
programmed
cell
death-1
(PD-L1)
downregulation
is
reported.
Upon
systemic
administration,
Cu/TI
accumulates
tumor
tissues
induce
immunogenic
cancer
death
reduce
PD-L1
expression.
Consequently,
promotes
the
intratumoral
infiltration
activation
cytotoxic
T
lymphocytes
greatly
inhibit
progression
colorectal
carcinoma
triple-negative
breast
mouse
models
without
causing
obvious
side
effects.
Abstract
Olefin‐linked
covalent
organic
frameworks
(OL‐COFs)
show
great
promise
for
visible‐light‐driven
photocatalysis.
Manipulating
atomic‐level
donor–acceptor
interactions
in
OL‐COFs
is
key
to
understanding
their
exciton
effects
this
system.
Here,
three
are
presented
with
orthorhombic
lattice
structures,
synthesized
via
Knoevenagel
polycondensation
reaction
of
terephthalaldehyde
and
tetratopic
monomers
featuring
phenyl,
benzo[c][1,2,5]oxadiazole,
benzo[c][1,2,5]thiadiazole
moieties.
These
feature
tunable
interactions,
making
them
ideal
studying
olefin‐linked
systems.
Comprehensive
analyses,
including
temperature‐dependent
photoluminescence
spectra,
ultrafast
spectroscopy,
theoretical
calculations,
reveal
that
stronger
lead
reduced
binding
energy
(
E
b
),
accelerated
dissociation,
longer‐lived
photogenerated
charges,
thereby
enhancing
photocatalytic
performance.
Notably,
The
TMO‐BDA
COF,
the
lowest
,
demonstrates
superior
activity
one‐pot
sequential
transformation
excellent
catalytic
performance
gram‐scale
reactions,
highlighting
its
potential
practical
applications.
This
work
provides
valuable
insights
into
regulating
effect
at
molecular
level
OL‐COFs,
offering
pathways
enhance
efficiency.
