Chinese Journal of Chemistry,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 28, 2024
Comprehensive
Summary
The
construction
of
luminescent
two‐dimensional
(2D)
imine‐linked
covalent
organic
frameworks
(COFs)
is
a
formidable
challenge
due
to
the
strong
interlayer
stacking
and
bond
rotations
that
typically
suppress
intramolecular
charge
transfer
(ICT),
leading
nonradiative
energy
dissipation.
Herein,
three
COFs
with
tailored
distances
are
designed
modulate
ICT
behaviours.
targeted
COF
(TPAZ‐TPE‐COF)
achieved
significantly
enhanced
photoluminescence
quantum
yield
(PLQY)
21.22%
in
solid
state
by
restricting
rotation
enlarging
layer
distance.
This
represents
3.5‐fold
530.5‐fold
improvement
over
TPAZ‐PYTA‐COF
(6.15%),
which
has
shortened
space,
TPAZ‐PATA‐COF
(0.04%),
exhibits
rotations,
respectively.
Importantly,
TPAZ‐TPE‐COF
also
exceptional
sensing
performance
for
iron
ions,
detection
limit
at
ppb
level.
Both
experimental
theoretical
analyses
reveal
prominent
assigned
effective
suppression
pathways,
especially
those
arising
from
vibrations.
These
findings
pave
way
deliberate
2D
high
PL
intensity,
thereby
expanding
portfolio
potential
applications
optoelectronics.
Angewandte Chemie,
Год журнала:
2024,
Номер
136(40)
Опубликована: Июнь 29, 2024
Abstract
Modulating
the
electronic
state
of
multicomponent
covalent
organic
framework
(COF)
electrocatalysts
is
crucial
for
enhancing
catalytic
activity.
However,
effect
dimensionality
on
their
physicochemical
functionalities
still
lacking.
Herein,
we
report
an
interlaced
unsaturated
2D
and
saturated
3D
strategy
to
develop
multicomponent‐regulated
COFs
with
tunable
gradient
high
selectivity
activity
electrocatalysis.
Compared
two‐component
model
COFs,
2D/3D
locally
irregular
dimensions
structures
are
more
practical
in
optimizing
intrinsic
electrode
surface
reaction
mass
transfer.
Remarkably,
2D‐inserted
TAE‐COF
regulates
adsorption
mode
OOH*
species
supply
a
favorable
dynamic
pathway
H
2
O
process,
thereby
achieving
excellent
production
rate
8.50
mol
g
cat
−1
h
.
Moreover,
utilizing
theoretical
calculation
situ
ATR‐FTIR
experiment,
found
that
central
carbon
atom
tetraphenyl‐based
unit
(site‐1
site‐6)
potential
active
sites.
This
operating
ability
reactants
dimensionality‐interconnected
building
blocks
provides
idea
designing
durable
efficient
electrocatalysts.
Chinese Journal of Chemistry,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 28, 2024
Comprehensive
Summary
The
construction
of
luminescent
two‐dimensional
(2D)
imine‐linked
covalent
organic
frameworks
(COFs)
is
a
formidable
challenge
due
to
the
strong
interlayer
stacking
and
bond
rotations
that
typically
suppress
intramolecular
charge
transfer
(ICT),
leading
nonradiative
energy
dissipation.
Herein,
three
COFs
with
tailored
distances
are
designed
modulate
ICT
behaviours.
targeted
COF
(TPAZ‐TPE‐COF)
achieved
significantly
enhanced
photoluminescence
quantum
yield
(PLQY)
21.22%
in
solid
state
by
restricting
rotation
enlarging
layer
distance.
This
represents
3.5‐fold
530.5‐fold
improvement
over
TPAZ‐PYTA‐COF
(6.15%),
which
has
shortened
space,
TPAZ‐PATA‐COF
(0.04%),
exhibits
rotations,
respectively.
Importantly,
TPAZ‐TPE‐COF
also
exceptional
sensing
performance
for
iron
ions,
detection
limit
at
ppb
level.
Both
experimental
theoretical
analyses
reveal
prominent
assigned
effective
suppression
pathways,
especially
those
arising
from
vibrations.
These
findings
pave
way
deliberate
2D
high
PL
intensity,
thereby
expanding
portfolio
potential
applications
optoelectronics.
