Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Oct. 10, 2024
Abstract
Covalent
organic
frameworks
(COFs)
have
garnered
growing
interest
in
the
field
of
biomedicine;
however,
their
application
sonodynamic
therapy
remains
underexplored
due
to
limited
understanding
intrinsic
activity
and
structure–property
relationships.
Here,
we
present
a
pore
wall
chemistry
modulation
strategy
for
empowering
two‐dimensional
(2D)
COF
heterojunctions
through
situ
growth
COFs
on
bismuth
oxycarbonate
nanosheets
(B
NSs).
Compared
negligible
effects
observed
pristine
B
NSs,
2D
heterojunction
with
vinyl‐decorated
walls
demonstrates
3.6‐fold
enhancement
sonocatalytic
singlet
oxygen
generation.
This
performance
also
significantly
outperforms
that
isoreticular
functionalized
methoxy
or
non‐substituted
groups.
Mechanistic
studies
reveal
vinyl
groups
B@COF
(BC)
facilitate
separation
transfer
charge
carriers
while
enhancing
adsorption
molecules.
Furthermore,
peroxymonosulfate
(PMS)
loading
into
porous
boosts
therapeutic
efficacy
antitumor
nanotherapy
via
dual
oxidative
species
These
findings
underscore
critical
role
modulating
properties
COFs,
advance
development
COF‐based
sonosensitizers
pro‐oxidative
applications.
Small,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 19, 2025
Abstract
The
porphyrin‐based
hydrogen‐bonded
organic
framework
(HOF)
offers
a
superior
platform
for
decoding
electrochemiluminescence
(ECL)
via
controlling
charge
transfer
due
to
its
higher
solubility,
chemical
stability,
and
tunable
behavior.
In
this
research,
three
kinds
of
HOFs
including
TDPP‐HOF,
TCPP‐HOF,
TCNPP‐HOF
are
synthesized
based
on
porphyrin
tectonic
plate
decorated
with
2,4‐diaminotriazinyl
(DAT),
carboxyl,
nitrile
moieties
study
their
ECL
performances.
hydrazine
as
the
coreactant
can
trigger
TDPP‐HOF
at
low‐excited
positive
potential
generate
15.8‐
112.9‐fold
enhancement
in
signal
than
TCPP‐HOF.
Experimental
results
density
functional
theory
calculations
verify
that
lower
bandgap
larger
binding
energy
(ΔE)
between
HOF
is
beneficial
intrareticular
(ICT),
facilitating
performance.
These
indicate
peripheral
substituents
establish
specialized
outer‐sphere
microenvironment
around
center
tune
both
activity
As
proof
concept,
simple
TDPP‐HOF‐based
sensor
constructed
sensitively
detect
phenolic
compounds.
This
research
provides
new
avenue
improving
performance
modulating
HOFs.
ACS Applied Materials & Interfaces,
Journal Year:
2025,
Volume and Issue:
17(9), P. 14623 - 14633
Published: Feb. 21, 2025
Photoluminescence
efficiencies
of
covalent
organic
frameworks
(COFs)
are
significantly
restricted
by
electron
delocalization
and
charge
transfer
among
the
conjugated
skeletons.
Two
nanofilms
using
tetraphenylethylene
benzo[c][1,2,5]thiadiazole
as
building
blocks
were
facilely
prepared
via
an
interfacially
confined
condensation
strategy.
The
distinct
dipole
moment
orientations
imine
linkages
involved
in
π-delocalization
donor-acceptor
systems
diversely.
They
also
played
critical
roles
affecting
fluorescence
turn-on
sensing
obtained
for
gaseous
trifluoroacetic
acid
(TFA).
joint
donor-C═N-acceptor
sequence
nanofilm
#2
resulted
relatively
stronger
originally
than
that
#1,
featuring
disturbed
donor-N═C-acceptor
sequence.
While
after
blowing
trace
TFA,
latter
#1
possessed
prominent
enhancement
obvious
color
visualization.
Comparative
transient
absorption
observations
theoretical
calculations
elucidated
effective
manipulation
intramolecular
(ICT)
imine-linked
functional
With
help
a
laminated
fluorescent
sensor,
compact
platform
was
further
integrated
optimized
#1.
It
exhibited
good
selectivity,
excellent
reversibility
(≥50
recycles),
extraordinary
detection
limit
(∼0.1
ppt),
rapid
recovery
process
to
TFA.
Our
findings
provide
valuable
optimizations
π-linkages
COFs
reliable
film
sensors
monitoring
toxic
hazardous
gases.
Covalent
organic
frameworks
(COFs)
serve
as
an
outstanding
platform
for
heterogeneous
photocatalysis.
We
synthesized
two
analogous
pyrene-based
two-dimensional
COFs
with
π-conjugated
networks,
one
linked
by
C═N
bonds
and
the
other
C═C
bonds,
through
Schiff
base
Knoevenagel
condensation
reactions,
respectively.
investigated
impact
of
these
linkages
on
photocatalytic
activity
COFs,
using
visible-light-mediated
thioesterification
a
model
reaction.
It
was
found
that
olefin-linkage
COF
outperformed
imine-linkage
photocatalyst.
The
developed
protocol
demonstrated
broad
substrate
scope,
including
35
diverse
carboxylic
acids,
14
drug
molecules,
several
disulfide
coupling
partners,
achieving
up
to
95%
yield
thioesters.
practical
utility
this
strategy
is
further
its
successful
application
in
gram-scale
reactions.
photocatalyst
robust
successfully
reused
multiple
cycles
without
any
loss
catalytic
activity.
backbone
facilitated
enhanced
electron
transfer
upon
light
irradiation,
enabling
cross-coupling
acid
reductive
cycle.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 27, 2025
Covalent
organic
frameworks
(COFs)
have
attracted
broad
interest
because
of
their
well-defined,
customizable,
highly
stable,
and
porous
structures.
COFs
shown
significant
potential
for
various
practical
applications,
such
as
gas
storage/purification,
drug
purification,
water
treatment,
catalysis,
battery
applications.
Scaling
up
is
desirable
to
meet
industrial
application
demands
but
hindered
by
the
limitations
synthesis
methods
high
cost
reactants.
Recently,
emerging
green
methods,
mechanochemical
flux
synthesis,
offered
promising
solutions
these
challenges
(e.g.,
ton-scale
production
has
been
achieved
companies
recently).
This
Perspective
provides
an
overview
state
art
with
respect
discusses
factors
influencing
large-scale
COFs.
Directions
opportunities
improving
performance
sustainability
toward
applications
are
also
emphasized.
Advanced Materials,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 20, 2025
Abstract
Covalent
organic
frameworks
(COFs)
are
emerging
as
a
transformative
platform
for
photocatalytic
hydrogen
peroxide
(H
2
O
)
production
due
to
their
highly
ordered
structures,
intrinsic
porosity,
and
molecular
tunability.
Despite
potential,
the
inefficient
utilization
of
photogenerated
charge
carriers
in
COFs
significantly
restrains
efficiency.
This
study
presents
two
regioisomeric
COFs,
α
‐TT‐TDAN
COF
β
COF,
both
incorporating
thieno[3,2‐b]thiophene
moieties,
investigate
influence
regioisomerism
on
excited
electron
distribution
its
impact
performance.
The
demonstrates
remarkable
solar‐to‐chemical
conversion
efficiency
1.35%,
outperforming
‐isomeric
counterpart,
which
is
merely
0.44%.
Comprehensive
spectroscopic
computational
investigations
reveal
critical
role
subtle
substitution
change
electronic
properties.
structural
adjustment
intricately
connects
structure
dynamics,
enabling
precise
regulation
distribution,
efficient
separation
transport,
localization
electrons
at
active
sites.
Moreover,
this
finely
tuned
interplay
enhances
oxygen
reduction
reaction.
These
findings
establish
new
paradigm
design,
offering
molecular‐level
strategy
advance
reticular
materials
toward
energy
conversion.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Aug. 13, 2024
Abstract
Development
of
highly
porous
and
robust
hydrogen‐bonded
organic
frameworks
(HOFs)
for
high‐pressure
methane
hydrogen
storage
remains
a
grand
challenge
due
to
the
fragile
nature
bonds.
Herein,
we
report
strategy
constructing
double‐walled
framework
target
HOF
(ZJU‐HOF‐5a)
extraordinary
CH
4
H
2
storage.
ZJU‐HOF‐5a
features
minimized
twofold
interpenetration
with
structure,
in
which
multiple
supramolecular
interactions
are
existed
between
interpenetrated
walls.
This
structural
configuration
can
notably
enhance
robustness
while
maintaining
its
high
porosity,
affording
one
highest
gravimetric
volumetric
surface
areas
3102
m
g
−1
1976
cm
−3
among
reported
HOFs
so
far.
thus
exhibits
an
extremely
uptake
43.6
L
at
77
K/100
bar
working
capacity
41.3
under
combined
swing
conditions
(77
bar→160
K/5
bar),
also
impressive
performance
5–100
187
(or
159)
3
(STP)
270
K
296
K),
outperforming
most
materials.
Single‐crystal
X‐ray
diffraction
studies
on
‐loaded
reveal
that
abundant
binding
sites
ultrahigh
porosities
account
capacities.
Combined
stability,
super‐hydrophobicity,
easy
recovery,
is
placed
promising
materials
applications.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Oct. 10, 2024
Abstract
Covalent
organic
frameworks
(COFs)
have
garnered
growing
interest
in
the
field
of
biomedicine;
however,
their
application
sonodynamic
therapy
remains
underexplored
due
to
limited
understanding
intrinsic
activity
and
structure–property
relationships.
Here,
we
present
a
pore
wall
chemistry
modulation
strategy
for
empowering
two‐dimensional
(2D)
COF
heterojunctions
through
situ
growth
COFs
on
bismuth
oxycarbonate
nanosheets
(B
NSs).
Compared
negligible
effects
observed
pristine
B
NSs,
2D
heterojunction
with
vinyl‐decorated
walls
demonstrates
3.6‐fold
enhancement
sonocatalytic
singlet
oxygen
generation.
This
performance
also
significantly
outperforms
that
isoreticular
functionalized
methoxy
or
non‐substituted
groups.
Mechanistic
studies
reveal
vinyl
groups
B@COF
(BC)
facilitate
separation
transfer
charge
carriers
while
enhancing
adsorption
molecules.
Furthermore,
peroxymonosulfate
(PMS)
loading
into
porous
boosts
therapeutic
efficacy
antitumor
nanotherapy
via
dual
oxidative
species
These
findings
underscore
critical
role
modulating
properties
COFs,
advance
development
COF‐based
sonosensitizers
pro‐oxidative
applications.
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
unknown
Published: June 6, 2024
Abstract
Proton
conduction
is
important
in
both
fundamental
research
and
technological
development.
Here
we
report
designed
synthesis
of
crystalline
porous
covalent
organic
frameworks
as
a
new
platform
for
high‐rate
anhydrous
proton
conduction.
By
developing
nanochannels
with
different
topologies
pathways
loading
neat
phosphoric
acid
to
construct
robust
carrier
networks
the
pores,
found
that
pore
topology
crucial
Its
effect
on
increasing
conductivity
an
exponential
mode
other
than
linear
fashion,
endowing
materials
exceptional
conductivities
exceeding
10
−2
S
cm
−1
over
broad
range
temperature
low
activation
energy
barrier
down
0.24
eV.
Remarkably,
size
controls
mechanism,
where
mesopores
promote
via
fast‐hopping
while
micropores
follow
sluggish
vehicle
process.
Notably,
decreasing
content
drastically
reduces
greatly
increases
barrier,
emphasizing
pivotal
role
well‐developed
network
transport.
These
findings
insights
unveil
general
transformative
guidance
designing
framework
systems
ion
conduction,
storage,
conversion.
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(45)
Published: July 18, 2024
Abstract
Helicenes
represent
a
class
of
fascinating
π
compounds
with
fused
yet
folded
backbones.
Despite
their
broad
structural
diversity,
harnessing
helicenes
to
develop
well‐defined
materials
is
still
formidable
challenge.
Here
we
report
the
synthesis
crystalline
porous
helicene
by
exploring
synthesize
covalent
2D
lattices
and
layered
frameworks.
Topology‐directed
polymerization
[6]helicenes
porphyrin
creates
networks
alternate
helicene‐porphyrin
alignment
along
x
y
directions
at
1.5‐nm
interval
develops
[6]helicene
frameworks
through
reversed
anti‐AA
stack
z
direction
form
segregated
columnar
arrays.
Notably,
this
configuration
enables
be
highly
red
luminescent
benchmark
quantum
yields.
The
trigger
effieicnt
intra‐framework
singlet‐to‐singlet
state
energy
transfer
from
facilitate
intermolecular
triplet‐to‐triplet
molecular
oxygen
produce
reactive
species,
harvesting
wide
range
photons
ultraviolet
near‐infrared
regions
for
light
emitting
photo‐to‐chemical
conversion.
This
study
introduces
new
family
extended
frameworks,
laying
groundwork
unprecedented
structures
functions.
