Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(47)
Published: Sept. 14, 2022
Abstract
Covalent
organic
frameworks
(COFs)
are
an
emerging
category
of
polymers
with
highly
porous
crystalline
structures.
In
the
last
decade,
reports
on
use
COFs
as
heterogeneous
photocatalysts
for
transformations
have
shown
significant
progress.
Still,
comprehensive
reviews
mechanisms
photocatalytic
using
lacking.
This
Review
provides
a
and
systematic
overview
COF‐based
transformations.
Firstly,
we
discuss
photophysical
properties
characterization
methods
photocatalysts.
Then,
general
mechanism,
advantages,
strategies
to
improve
efficiency
summarized.
After
that,
advanced
examples
analyzed
regard
underlying
mechanisms.
The
ends
critical
perspective
challenges
prospects.
Advanced Materials,
Journal Year:
2022,
Volume and Issue:
35(24)
Published: Dec. 23, 2022
Abstract
Organic
photochemistry
is
intensely
developed
in
the
1980s,
which
nature
of
excited
electronic
states
and
energy
electron
transfer
processes
are
thoroughly
studied
finally
well‐understood.
This
knowledge
from
molecular
organic
can
be
transferred
to
design
covalent
frameworks
(COFs)
as
active
visible‐light
photocatalysts.
COFs
constitute
a
new
class
crystalline
porous
materials
with
substantial
application
potentials.
Featured
outstanding
structural
tunability,
large
porosity,
high
surface
area,
excellent
stability,
unique
photoelectronic
properties,
potential
candidates
various
research
areas
(e.g.,
photocatalysis).
review
aims
provide
state‐of‐the‐art
insights
into
COF
photocatalysts
(pristine,
functionalized,
hybrid
COFs)
for
transformations.
The
catalytic
reaction
mechanism
COF‐based
influence
dimensionality
crystallinity
on
heterogenous
photocatalysis
performance
also
discussed,
followed
by
perspectives
prospects
main
challenges
opportunities
future
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(32)
Published: June 8, 2022
Covalent
organic
frameworks
(COFs)
are
appealing
photocatalysts
for
toxic
chemical
degradation.
Great
efforts
have
been
devoted
to
regulate
the
photocatalytic
performance
of
COFs
by
tuning
their
building
blocks,
but
relationship
between
COF
linkage
and
photochemical
properties
has
rarely
explored.
Herein,
we
report
synthesis
characterisation
a
novel
aminal-linked
porphyrinic
COF,
namely
Por-Aminal-COF.
Por-Aminal-COF
(0.25
mol
%)
showed
excellent
activity
toward
detoxification
sulfur
mustard
simulant
with
half-life
(t1/2
)
5
min,
which
is
far
lower
than
that
traditional
imine-linked
Por-COF
=16
min).
Transient
absorption
spectroscopy
indicated
aminal
linkages
facilitated
intersystem
crossing
process.
Thus,
higher
triplet-state
generation
efficiency
compared
Por-COF,
consequently
promoting
activation
oxygen
molecular
singlet
oxygen.
Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: Feb. 17, 2024
Abstract
The
direct
use
of
flue
gas
for
the
electrochemical
CO
2
reduction
reaction
is
desirable
but
severely
limited
by
thermodynamically
favorable
oxygen
reaction.
Herein,
a
photonicswitching
unit
1,2-Bis(5’-formyl-2’-methylthien-3’-yl)cyclopentene
(DAE)
integrated
into
cobalt
porphyrin-based
covalent
organic
framework
highly
efficient
electrocatalysis
under
aerobic
environment.
DAE
moiety
in
material
can
reversibly
modulate
O
activation
capacity
and
electronic
conductivity
ring-closing/opening
reactions
UV/Vis
irradiation.
DAE-based
with
ring-closing
type
shows
high
Faradaic
efficiency
90.5%
partial
current
density
−20.1
mA
cm
−2
at
−1.0
V
vs.
reversible
hydrogen
electrode
co-feeding
5%
.
This
work
presents
an
passivation
strategy
to
realize
electroreduction
performance
,
which
would
inspire
design
electrocatalysts
practical
source
such
as
from
power
plants
or
air.
Nature Communications,
Journal Year:
2023,
Volume and Issue:
14(1)
Published: June 23, 2023
Abstract
Controlling
the
number
of
molecular
switches
and
their
relative
positioning
within
porous
materials
is
critical
to
functionality
properties.
The
proximity
many
one
another
can
hinder
or
completely
suppress
response.
Herein,
a
synthetic
strategy
involving
mixed
linkers
used
control
distribution
spiropyran-functionalized
in
covalent
organic
framework
(COF).
COF
contains
spiropyran
each
pore
which
exhibits
excellent
reversible
photoswitching
behavior
its
merocyanine
form
solid
state
response
UV/Vis
light.
spiro-COF
possesses
an
urchin-shaped
morphology
morphological
transition
2D
nanosheets
vesicles
solution
upon
UV
light
irradiation.
merocyanine-equipped
COFs
are
extremely
stable
possess
more
ordered
structure
with
enhanced
photoluminescence.
This
approach
modulating
structural
isomerization
develop
inkless
printing
media,
while
photomediated
polarity
change
for
water
harvesting
applications.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(29)
Published: March 30, 2023
Abstract
The
advances
made
in
the
field
of
stimuli‐responsive
catalysis
during
last
five
years
with
a
focus
on
novel
recently‐emerged
directions
and
applications
have
been
surveyed.
Metal‐free
catalysts
organometallic
complexes,
as
well
biomimetic
systems
extended
structures,
which
display
switchable
catalytic
activity
for
variety
organic
transformations,
are
discussed.
Light‐activated
comprised
photochromic
molecules
capable
modulating
reaction
rate,
yield,
or
enantioselectivity
based
geometric
electronic
changes
associated
photoisomerization
detailed
discussion.
Alternative
stimuli,
including
pH
temperature,
could
be
applied
either
alone
combination
light,
also
addressed.
Recent
clearly
demonstrate
that
capability
to
finely
tune
catalyst
behavior
via
an
external
stimulus
is
powerful
tool
alter
landscape
sustainable
chemistry.
Accounts of Chemical Research,
Journal Year:
2022,
Volume and Issue:
55(21), P. 3136 - 3149
Published: Oct. 19, 2022
ConspectusPhotochromic
diarylethenes
featuring
reversible
regulation
by
external
light
irradiation
have
attracted
increasing
attention
in
versatile
applications
such
as
logic
gates,
supramolecular
systems,
liquid
crystals,
and
super-resolution
imaging
because
of
their
outstanding
bistability
fatigue
resistance.
However,
for
typical
diarylethene
there
always
exist
three
unsolved
issues.
The
first
is
how
to
modulate
the
between
open
closed
forms
from
viewpoint
ethene
bridge
aromaticity.
second
decrease
avoid
photoinactive
parallel
conformer
order
achieve
a
high
quantum
yield,
since
form
possesses
photoactive
antiparallel
(ap)
conformation
(p)
conformation.
Because
rapid
rotation
flexible
side
aryl
groups,
two
conformers
cannot
be
separated
efficiently,
thereby
resulting
relatively
low
photocyclization
yield.
third
fulfill
enantiospecific
transformation
with
reversibility
photomodulate
chirality.
Stereochemically,
ap
C2
symmetry
can
further
subdivided
into
pair
enantiomers
P
M
helicity
originating
central
hexatriene
moiety.
Similarly,
also
lead
loss
intrinsic
chirality,
restricting
development
application
light-driven
chiroptical
switches.
Accordingly,
it
desirable
construct
specific
system
break
through
these
bottlenecks
real
applications.Our
group
has
recently
developed
unique
sterically
hindered
based
on
benzobis(thiadiazole)
completely
solving
We
introduce
low-aromaticity
unit
incomparably
bistability.
To
block
or
freeze
aryls,
we
incorporate
large
bulky
benzothiophene
induce
steric
hindrance,
barrier,
successfully
separating
multiple
yields
photoreaction.
Consequently,
given
fantastic
building
block,
enhance
its
performance
means
self-assembly,
realizing
conformer-dependent
self-assembly
well
unprecedented
concerted
isomerization
photoreaction
photoresponsive
metallacycles.
In
addition,
decoration
intrinsically
chiral
mesogenic
units
enable
us
manipulate
helical
superstructure
thus
achieving
anticounterfeiting
technique
quadridimensional
manipulable
laser.
unravel
dual
aggregation-induced
emission
(AIE)
behavior
diarylethene,
especially
applied
imaging.
Chemical Science,
Journal Year:
2022,
Volume and Issue:
13(28), P. 8253 - 8264
Published: Jan. 1, 2022
The
incorporation
of
molecular
machines
into
the
backbone
porous
framework
structures
will
facilitate
nano
actuation,
enhanced
transport,
and
other
out-of-equilibrium
host-guest
phenomena
in
well-defined
3D
solid
materials.
In
this
work,
we
detail
synthesis
a
diamine-based
light-driven
motor
its
series
imine-based
polymers
covalent
organic
frameworks
(COF).
We
study
structural
dynamic
properties
building
blocks
derived
self-assembled
solids
with
spectroscopic,
diffraction,
theoretical
methods.
Using
an
acid-catalyzed
approach,
are
able
to
obtain
first
crystalline
2D
COF
stacked
hexagonal
layers
that
contains
20
mol%
motors.
features
specific
pore
volume
surface
area
up
0.45
cm3
g-1
604
m2
g-1,
respectively.
Given
structure
bulkiness
diamine
motor,
supramolecular
assembly
stacking
disorders
between
adjacent
layers.
finally
probe
dynamics
situ
spectroscopic
techniques
revealing
current
limitations
analysis
these
new
materials
derive
important
design
criteria
as
well
synthetic
access
generations
motorized
