Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(20), P. 14128 - 14135
Published: May 9, 2024
The
transformation
of
two-dimensional
(2D)
covalent–organic
frameworks
(COFs)
into
three-dimensions
(3D)
is
synthetically
challenging,
and
it
typically
addressed
through
interlayer
cross-linking
alkene
or
alkyne
bonds.
Here,
we
report
the
first
example
chemical
reconstruction
a
2D
COF
to
3D
with
complete
lattice
rearrangement
facilitated
by
base-triggered
boron
hybridization.
This
involves
conversion
trigonal
boronate
ester
linkages
tetrahedral
anionic
spiroborate
linkages.
reticulates
coplanar,
closely
stacked
square
cobalt(II)
phthalocyanine
(PcCo)
units
perpendicular
arrangement.
As
result,
pore
size
COFs
expands
from
2.45
nm
for
initial
(sql)
3.02
in
noninterpenetrated
network
(nbo).
Mechanistic
studies
reveal
base-catalyzed
protodeboronation
pathway
formation
structure.
Advanced Functional Materials,
Journal Year:
2023,
Volume and Issue:
34(1)
Published: Sept. 21, 2023
Abstract
Adsorption‐photocatalysis
technology
based
on
covalent
organic
frameworks
(COFs)
offers
an
alternative
method
for
advancing
the
field
of
uranium
extraction
from
seawater.
When
determining
photocatalytic
activity
COFs,
binding
energy
excitons
(
E
b
)
functions
is
decisive
factor.
Nevertheless,
majority
reported
COFs
have
a
large
,
which
seriously
restricts
their
application
in
photocatalysis.
Using
practical
π‐skeleton
engineering
strategy,
current
study
synthesizes
three
donor‐acceptor
olefin‐linked
containing
amidoxime
units
effort
to
minimize
.
Theoretical
and
experimental
results
reveal
that
construction
planar
continuous
π
‐electron
delocalization
channels
can
significantly
reduce
promote
separation
electron‐hole
pairs,
thereby
enhancing
activities.
Moreover,
TTh‐COF‐AO
with
‐skeleton
donor
reduced,
exhibits
substantially
smaller
(38.4
meV).
Under
visible
light
irradiation,
high
photo‐enhanced
capacity
10.24
mg
g
−1
achieved
natural
seawater
without
addition
sacrificial
reagents,
superior
been
date.
This
study,
therefore,
paves
way
development
tailored,
efficient
photocatalysts
Chemical Reviews,
Journal Year:
2024,
Volume and Issue:
124(12), P. 7829 - 7906
Published: June 3, 2024
Covalent
network
polymers,
as
materials
composed
of
atoms
interconnected
by
covalent
bonds
in
a
continuous
network,
are
known
for
their
thermal
and
chemical
stability.
Over
the
past
two
decades,
these
have
undergone
significant
transformations,
gaining
properties
such
malleability,
environmental
responsiveness,
recyclability,
crystallinity,
customizable
porosity,
enabled
development
integration
dynamic
chemistry
(DCvC).
In
this
review,
we
explore
innovative
realm
polymers
focusing
on
recent
advances
achieved
through
application
DCvC.
We
start
examining
history
fundamental
principles
DCvC,
detailing
its
inception
core
concepts
noting
key
role
reversible
bond
formation.
Then
reprocessability
DCvC
is
thoroughly
discussed,
starting
from
milestones
that
marked
evolution
progressing
to
current
trends
applications.
The
influence
crystallinity
then
reviewed,
covering
diversity,
synthesis
techniques,
functionalities.
concluding
section,
address
challenges
faced
field
speculates
potential
future
directions.
Advanced Functional Materials,
Journal Year:
2024,
Volume and Issue:
unknown
Published: March 10, 2024
Abstract
Covalent
organic
frameworks
(COFs)
attract
significant
attention
due
to
their
ordered,
crystalline,
porous,
metal‐free,
and
predictable
structures.
These
unique
characteristics
offer
great
opportunities
for
the
diffusion
transmission
of
photogenerated
charges
during
photocatalysis.
Currently,
a
considerable
number
COFs
are
used
as
metal‐free
semiconductor
photocatalysts.
This
review
aims
understand
relationships
between
structure
photocatalysis
performance
provides
in‐depth
insight
into
synthetic
strategy
improve
performance.
Subsequently,
focuses
on
structural
motif
in
sustainable
photocatalytic
hydrogen
evolution,
carbon
dioxide
reduction,
peroxide
generation,
compound
transformations.
Last,
conjunction
with
progress
achieved
challenges
yet
be
overcome,
candid
discussion
is
undertaken
regarding
field
COF
photocatalysis,
accompanied
by
presentation
potential
research
avenues
future
directions.
seeks
provide
readers
comprehensive
understanding
pivotal
role
robust
guidance
innovative
utilization
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(7), P. 4728 - 4737
Published: March 13, 2024
Imine-linked
isomeric
covalent
organic
frameworks
(COFs)
with
opposite
linkage
orientations
are
not
rare,
but
their
structure
and
photocatalytic
property
corrections
still
puzzling,
let
alone
the
emerging
photosynthetic
H2O2
performance.
Herein,
a
pair
of
COFs
(TB-COF
TA-COF)
reversed
imine
linkages
was
fabricated.
Compared
to
TA-COF,
TB-COF
exhibited
larger
dipole
moments
better
charge
carrier
separation
efficiency,
resulting
in
superior
photosynthesis
capability
via
dominant
oxygen
reduction
reaction
(ORR)
paths
(O2–O2•––H2O2
O2–O2•––O21–H2O2)
feeble
water
oxidation
(WOR)
paths.
With
no
sacrificial
agents
air,
rates
were
5186
μmol
g–1
h–1
4111
natural
seawater,
respectively.
The
seawater-produced
can
be
directly
utilized
for
tetracycline
degradation,
manifesting
big
picture
wastewater
treatment
by
H2O2.
Theoretical
calculations
revealed
that
hydroxyl-rich
benzene
ring
photooxidation
part
triazine
unit
primary
photoreduction
part.
Through
linkage-orientation
regulation,
electronic
structures,
migration
property,
energy
barrier
rate
determination
step
2e–
ORR
WOR
well-modulated.
current
work
provides
insight
into
effect
orientation
on
performance
may
enlighten
design
catalysts
photosynthesis.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(6), P. 3778 - 3787
Published: Feb. 22, 2024
In
recent
years,
significant
progress
has
been
achieved
in
the
field
of
three-dimensional
covalent
organic
frameworks
(3D
COFs).
However,
there
is
still
a
great
challenge
to
use
flexible
building
units
synthesize
high-connectivity
3D
COFs.
this
work,
we
showed
that
[6
+
3]
COFs
could
be
constructed
by
inducing
highly
planar
blocks
from
C3
antitriangular
prismed
blocks.
Herein,
two
with
spn
topology
based
on
cyclotriphosphazene
were
and
denoted
as
TAA/TAB-CTP-COF,
their
redox
ability
photophysical
features
can
finely
regulated
coupled
functional
group,
such
benzene
triazine
groups.
As
result,
heteromotif
molecular
junction
TAA-CTP-COF
fully
exposed
active
sites
high
photocatalytic
production
hydrogen
peroxide
(H2O2)
yield
1041
μM
h–1
without
any
additional
photosensitizers,
scavengers,
or
cocatalysts.
Furthermore,
presence
an
electron
donor,
rate
H2O2
reach
up
2221
h–1,
exhibiting
one
best
performances
for
crystalline
materials.
This
work
showcases
potential
using
highlights
versatility
efficacy
metal-free
solar
energy
conversion.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(5), P. 3373 - 3382
Published: Jan. 25, 2024
Reticular
chemistry
effectively
yields
porous
structures
with
distinct
topological
lattices
for
a
broad
range
of
applications.
Polyhedral
oligomeric
silsesquioxane
(POSS)-based
octatopic
building
blocks
rare
Oh
symmetric
configuration
and
attracting
inorganic
features
have
great
potential
creating
three-dimensional
(3D)
covalent
organic
frameworks
(COFs)
new
topologies.
However,
the
intrinsic
flexibility
intensive
motion
cubane-type
POSS
molecules
make
construction
3D
regular
challenging.
Herein,
by
fastening
three
or
four
cores
per
aromatic
rigid
linker
from
rational
steric
directions,
we
successfully
developed
serial
crystalline
COFs
unpresented
"the"
scu
Both
experimental
theoretical
results
proved
formation
target
POSS-based
COFs.
The
resultant
hybrid
networks
designable
chemical
skeletons
high
surface
areas
maintain
superiorities
both
components,
such
as
their
compatibility
salts,
abundant
periodic
electroactive
sites,
excellent
thermal
stability,
open
multilevel
nanochannels.
Consequently,
polycubane
could
serve
outstanding
solid
electrolytes
ionic
conductivity
1.23
×
10–4
S
cm–1
lithium-ion
transference
number
0.86
at
room
temperature.
This
work
offers
pathway
to
generate
ordered
multiconnected
flexible
cube
motifs
enrich
topologies
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(12)
Published: Feb. 1, 2024
The
topological
diversity
of
covalent
organic
frameworks
(COFs)
enables
considerable
space
for
exploring
their
structure-performance
relationships.
In
this
study,
we
report
a
sequence
novel
1D
COFs
(EO,
ES,
and
ESe-COF)
with
typical
4-c
sql
topology
that
can
be
interconnected
VIA
group
elements
(O,
S,
Se)
via
modular
design
strategy.
It
is
found
the
electronic
structures,
charge
delivery
property,
light
harvesting
ability,
hydrophilicity
these
profoundly
influenced
by
bridge-linked
atom
ordinal.
Finally,
EO-COF,
possessing
highest
quantity
active
sites,
longest
lifetime
electron,
strongest
interaction
O
Advanced Functional Materials,
Journal Year:
2024,
Volume and Issue:
34(25)
Published: Feb. 4, 2024
Abstract
Supramolecular
organic
framework
(SOF)
has
recently
garnered
significant
research
interest
in
the
field
of
luminescent
materials.
However,
SOF
with
room‐temperature
phosphorescence
emission
solution
is
very
rare
due
to
quenching
dissolved
oxygen
and
free
molecular
motions,
which
would
lead
nonradiative
deactivation
triplet
exciton
liquid
state.
In
this
work,
a
3D
cationic
phosphorescent
synthesized
through
host‐guest
interaction
between
CB[8]
tetrahedral
monomer
TBBP,
can
rapidly
adsorb
anionic
guests
solution.
When
dyes
are
introduced,
singlet
Förster
resonance
energy
transfer
(TS‐FRET)
be
achieved,
delayed
fluorescence
large
Stokes
shift
realized.
Additionally,
when
drugs
TBBP‐CB[8]
quenched
charge
transfer,
enabling
detection
signals.
Taking
advantage
fast
adsorption
property
SOF,
an
INHIBIT
logic
gate
three
inputs
two
outputs
constructed.
These
findings
provide
novel
method
prepare
functional
materials
new
pathway
construct
TS‐FRET
system
