Advanced Optical Materials,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 6, 2025
Abstract
In
order
to
inhibit
non‐radiative
decay
pathways
of
covalent‐organic
frameworks
(COFs),
a
strategy
is
proposed
block
intralayer
conjugation
and
interlayer
π–π
stacking
by
using
flexible
aggregation‐induced
emission
(AIE)
building
blocks
(4′,4′′′,4′′′′′,4′′′′′′′‐(1,2‐ethenediylidene)
tetrakis[1,1′‐biphenyl]‐4‐carbaldehyde
(TFBE))
connected
weakly
conjugated
linker.
By
the
TFBE
as
changing
flexibility
linker,
TFBE‐COFs
with
different
luminescence
properties
are
obtained.
Experimental
theoretical
results
show
that
these
have
high
crystallinity
large
layer
spacing,
among
which
photoluminescence
quantum
yield
hydrazone
(Hz)‐COF
TFBE‐ODH
(oxalyl
dihydrazide
(ODH))
in
solid
state
reaches
26.28%,
superior
most
COFs
reported
so
far.
The
excellent
attributed
non‐planar
geometry
TFBE,
inhibits
quenching.
Moreover,
π‐electron
delocalization‐induced
leaps
suppressed
further
enhances
TFBE‐COFs.
Hz‐COF
exhibits
sensing
performance
for
trace
tetracycline,
detection
limit
0.15
µ
m
.
addition,
white
light‐emitting
diodes
coated
manufactured
achieve
high‐quality
light
emission.
This
study
provides
new
design
application
high‐emission
COFs.
Nature Communications,
Journal Year:
2025,
Volume and Issue:
16(1)
Published: Feb. 24, 2025
Electrochemiluminescence
(ECL)
is
a
light-emitting
process
in
which
the
stability
of
electrochemically
generated
radicals
has
crucial
impact
on
efficiency
and
durability
excited
state
generation.
Therefore,
deciphering
relationship
between
radical
ECL
performance
highly
appealing.
In
this
work,
three
sp2
carbon-conjugated
covalent
organic
framework
(COF)
reticular
nanoemitters
compositing
same
pyrene
luminophores
but
different
acrylonitrile
linkers
are
designed
with
progressive
electron
affinities,
named
as
CN-COF-1,
2,
3.
By
precisely
modulating
affinity
CN-COFs,
volcano
discovered
78
folds
enhancement
intensity.
Density
functional
theoretical
calculations
indicate
that
CN-COF-2
exhibits
moderate
stabilization
capacity
well
efficient
transport
cores,
facilitating
Significantly,
appropriate
not
only
achieves
self-enhanced
cathodic
also
promotes
The
rational
regulation
paves
way
for
developing
decoding
fundamentals.
Deciphering
electrochemiluminescence
important
since
an
Here,
authors
describe
shaped
via
acrylonitrile-linked
frameworks.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(47), P. 32161 - 32205
Published: Nov. 18, 2024
Covalent
organic
frameworks
(COFs)
are
created
by
the
condensation
of
molecular
building
blocks
and
nodes
to
form
two-dimensional
(2D)
or
three-dimensional
(3D)
crystalline
frameworks.
The
diversity
with
different
properties
functionalities
large
number
possible
framework
topologies
open
a
vast
space
well-defined
porous
architectures.
Besides
more
classical
applications
materials
such
as
absorption,
separation,
catalytic
conversions,
interest
in
optoelectronic
COFs
has
recently
increased
considerably.
electronic
both
their
linkage
chemistry
can
be
controlled
tune
photon
absorption
emission,
create
excitons
charge
carriers,
use
these
carriers
photocatalysis,
luminescence,
chemical
sensing,
photovoltaics.
In
this
Perspective,
we
will
discuss
relationship
between
structural
features
properties,
starting
connectivity,
layer
stacking
2D
COFs,
control
over
defects
morphology
including
thin
film
synthesis,
exploring
theoretical
modeling
structural,
electronic,
dynamic
discussing
recent
intriguing
focus
on
photocatalysis
photoelectrochemistry.
We
conclude
some
remarks
about
present
challenges
future
prospects
powerful
architectural
paradigm.
ACS Materials Letters,
Journal Year:
2024,
Volume and Issue:
6(4), P. 1120 - 1129
Published: Feb. 26, 2024
Vinylene-linked
covalent–oganic
frameworks
(COFs),
as
novel
photocatalysts,
have
garnered
considerable
attention
due
to
their
exceptional
stability,
remarkable
π-electron
delocalization,
and
precisely
customizable
structures.
However,
the
design
of
monomers
for
constructing
vinylene-linked
COFs
with
tunable
electronic
structures
is
still
in
its
early
stages
poses
a
number
challenges.
Addressing
this,
tritopic
monomer
was
developed
by
attaching
3-fold
2-methylpyridine
unit
triphenyl-1,3,5-triazine
core.
The
further
condensed
aromatic
dialdehydes
via
solid-state
Knoevenagel
polycondensation
reaction
form
two
2D
(TP-PB
TP-PT
COF),
which
exhibited
excellent
crystallinity,
preeminent
outstanding
delocalization.
More
importantly,
modulation
donor–acceptor
(D–A)
interaction
within
COFs,
semiconducting
properties
could
be
optimized.
Due
stronger
D–A
interactions
TP-PB
COF
containing
1,3,5-triphenylbenzene
than
unit,
broader
visible
light
absorption,
narrower
band
gap,
photocurrent
response,
lower
charge
transfer
resistance,
makes
more
efficient
photocatalyst
photocatalytic
selective
conversions
organic
sulfides
sulfoxides
C-3
thiocyanation
indole
derivatives
high
catalytic
activity
recyclability.
This
work
not
only
demonstrates
construction
but
also
presents
facile
strategy
regulating
such
fine-tuning
matrices.
Small,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Sept. 9, 2024
Abstract
Covalent
organic
frameworks
(COFs)
have
emerged
as
one
of
the
most
studied
photocatalysts
owing
to
their
adjustable
structure
and
bandgaps.
However,
there
is
limited
research
on
regulating
light‐harvesting
capabilities
acceptor
building
blocks
in
donor–acceptor
(D–A)
isomer
COFs
with
different
bond
orientations.
This
investigation
crucial
for
elucidating
structure‐property‐performance
relationship
COF
photocatalysts.
Herein,
a
series
D–A
isostructural
are
synthesized
imine
orientations
using
benzothiadiazole
its
derivatives‐based
units.
Extended
light
absorption
achieved
groups
that
strong
electron‐withdrawing
capacities,
although
this
resulted
decreased
hydrogen
generation
efficiency.
Photocatalytic
experiments
indicated
dialdehyde
benzothiadiazole‐based
COFs,
HIAM‐0015,
exhibit
highest
rate
(17.99
mmol
g
−1
h
),
which
15
times
higher
than
isomer.
The
excellent
photocatalytic
performance
HIAM‐0015
can
be
attributed
fast
charge
separation
migration.
work
provides
insights
into
rational
design
synthesis
achieve
efficient
activity.
Small,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Nov. 3, 2024
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.
ACS Materials Letters,
Journal Year:
2023,
Volume and Issue:
6(1), P. 212 - 221
Published: Dec. 14, 2023
Vinylene-linked
covalent
organic
frameworks
(COFs)
are
considered
promising
heterogeneous
photocatalyst
candidates
for
synthesis
because
of
their
robust
and
conjugated
frameworks.
For
the
first
time,
a
series
vinylene-linked
COFs
decorated
by
halogen
atoms
(F,
Cl,
Br)
were
synthesized
further
utilized
as
photocatalysts
C–H
activation
reactions.
The
corresponding
optoelectronic
properties
could
be
precisely
regulated
via
modulation
functionalities
in
nanopore
channel
COFs.
It
is
worth
noting
that
unique
structures
make
these
effective
reactions
synthesis.
All
exhibited
extraordinary
catalytic
performance
reusability
functionalization
based
on
functionalities.
Especially,
highest
yield
was
achieved
photocatalytic
thiolation
1,4-naphthoquinones
with
Br-COF
suitable
conduction
band
position.
This
work
may
provide
new
scaffold
to
rationally
design
efficient
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(22)
Published: March 19, 2024
Abstract
Covalent
organic
frameworks
(COFs)
provide
a
molecular
platform
for
designing
novel
class
of
functional
materials
with
well‐defined
structures.
A
crucial
structural
parameter
is
the
linkage,
which
dictates
how
knot
and
linker
units
are
connected
to
form
two‐dimensional
polymers
layer
frameworks,
shaping
ordered
π‐array
porous
architectures.
However,
roles
linkage
in
development
π
electronic
structures
functions
remain
fundamental
yet
unresolved
issues.
Here
we
report
designed
synthesis
COFs
featuring
four
representative
linkages:
hydrazone,
imine,
azine,
C=C
bonds,
elucidate
their
impacts
on
evolution
functions.
Our
observations
revealed
that
hydrazone
provides
non‐conjugated
connection,
while
imine
azine
allow
partial
conjugation,
bond
permits
full
π‐conjugation.
Importantly,
profoundly
influences
control
functions,
unraveling
its
pivotal
role
determining
key
properties
such
as
band
gap,
frontier
energy
levels,
light
absorption,
luminescence,
carrier
density
mobility,
magnetic
permeability.
These
findings
highlight
significance
chemistry
offer
general
transformative
guidance
framework
achieve
