Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(26)
Published: April 16, 2024
Abstract
Electrically
conducting
two‐dimensional
(2D)
metal–organic
frameworks
(MOFs)
have
garnered
significant
interest
due
to
their
remarkable
structural
tunability
and
outstanding
electrical
properties.
However,
the
design
synthesis
of
high‐performance
materials
face
challenges
limited
availability
specific
ligands
pore
structures.
In
this
study,
we
employed
a
novel
highly
branched
D
3h
symmetrical
planar
conjugated
ligand,
dodechydroxylhexabenzotrinaphthylene
(DHHBTN)
fabricate
series
2D
conductive
MOFs,
named
M–DHHBTN
(M=Co,
Ni,
Cu).
This
new
family
MOFs
offers
two
distinct
types
pores,
elevating
complexity
more
advanced
level.
The
intricate
tessellation
patterns
are
elucidated
through
comprehensive
analyses
involving
powder
X‐ray
diffraction,
theoretical
simulations,
high‐resolution
transmission
electron
microscope.
Optical‐pump
terahertz‐probe
spectroscopic
measurements
unveiled
carrier
mobility
in
DHHBTN‐based
spanning
from
0.69
3.10
cm
2
V
−1
s
.
Among
famility,
Cu‐DHHBTN
displayed
high
conductivity
reaching
0.21
S
at
298
K
with
thermal
activation
behavior.
work
leverages
“branched
conjugation”
ligand
encode
heteroporosity
into
underscoring
potential
heterogeneous
double‐pore
structures
for
future
applications.
ACS Nano,
Journal Year:
2024,
Volume and Issue:
18(33), P. 21804 - 21835
Published: Aug. 8, 2024
Covalent
organic
frameworks
(COFs)
are
crystalline
networks
with
extended
backbones
cross-linked
by
covalent
bonds.
Due
to
the
semiconductive
properties
and
variable
metal
coordinating
sites,
along
rapid
development
in
linkage
chemistry,
utilization
of
COFs
photocatalytic
CO2RR
has
attracted
many
scientists'
interests.
In
this
Review,
we
summarize
latest
research
progress
on
for
CO2
reduction.
first
part,
present
COF
linkages
that
have
been
used
CO2RR,
discuss
four
mechanisms
including
as
intrinsic
photocatalysts,
photosensitive
motifs
metalated
semiconductors
heterojunction
photocatalysts.
Then,
principles
structural
designs
functional
building
units
stacking
mode
exchange.
Finally,
outlook
challenges
provided.
This
Review
is
intended
give
some
guidance
design
synthesis
diverse
different
linkages,
various
structures,
divergent
modes
efficient
photoreduction
CO2.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(24), P. 16681 - 16688
Published: June 5, 2024
Electrochemiluminescence
(ECL)
involves
charge
transfer
between
electrochemical
redox
intermediates
to
produce
an
excited
state
for
light
emission.
Ensuring
precise
control
of
is
essential
decoding
ECL
fundamentals,
yet
guidelines
on
how
achieve
this
conventional
emitters
remain
unexplored.
Molecular
ratchets
offer
a
potential
solution,
as
they
enable
the
directional
energy
or
chemicals
while
impeding
reverse
movement.
Herein,
we
designed
10
pairs
imine-based
covalent
organic
frameworks
reticular
delicately
manipulate
intrareticular
directing
transduction
from
electric
and
chemical
energies.
Aligning
donor
acceptor
(D–A)
directions
with
imine
dipole
effectively
facilitates
migration,
whereas
reversing
D–A
direction
impedes
it.
Notably,
ratchet
effect
directionality
intensified
increasing
contrast,
resulting
in
remarkable
680-fold
improvement
efficiency.
Furthermore,
dipole-controlled
exciton
binding
energy,
electron/hole
decay
kinetics,
femtosecond
transient
absorption
spectra
identified
electron
tendency
N-end
toward
C-end
during
transduction.
An
exponential
correlation
efficiency
difference
was
discovered.
Our
work
provides
general
approach
design
next-generation
devices.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(26)
Published: April 16, 2024
Abstract
Electrically
conducting
two‐dimensional
(2D)
metal–organic
frameworks
(MOFs)
have
garnered
significant
interest
due
to
their
remarkable
structural
tunability
and
outstanding
electrical
properties.
However,
the
design
synthesis
of
high‐performance
materials
face
challenges
limited
availability
specific
ligands
pore
structures.
In
this
study,
we
employed
a
novel
highly
branched
D
3h
symmetrical
planar
conjugated
ligand,
dodechydroxylhexabenzotrinaphthylene
(DHHBTN)
fabricate
series
2D
conductive
MOFs,
named
M–DHHBTN
(M=Co,
Ni,
Cu).
This
new
family
MOFs
offers
two
distinct
types
pores,
elevating
complexity
more
advanced
level.
The
intricate
tessellation
patterns
are
elucidated
through
comprehensive
analyses
involving
powder
X‐ray
diffraction,
theoretical
simulations,
high‐resolution
transmission
electron
microscope.
Optical‐pump
terahertz‐probe
spectroscopic
measurements
unveiled
carrier
mobility
in
DHHBTN‐based
spanning
from
0.69
3.10
cm
2
V
−1
s
.
Among
famility,
Cu‐DHHBTN
displayed
high
conductivity
reaching
0.21
S
at
298
K
with
thermal
activation
behavior.
work
leverages
“branched
conjugation”
ligand
encode
heteroporosity
into
underscoring
potential
heterogeneous
double‐pore
structures
for
future
applications.
Angewandte Chemie International Edition,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 9, 2025
Photo/electro-catalytic
CO2
reduction
into
high-value
products
are
promising
strategies
for
addressing
both
environmental
problems
and
energy
crisis.
Duo
to
their
advantageous
visible
light
absorption
ability,
adjustable
optic/electronic
properties,
definite
active
center,
post-modification
capability,
excellent
stability,
porphyrin-based
covalent
organic
frameworks
(COFs)
have
emerged
as
attractive
photo/electro-catalysts
towards
reduction.
In
this
review,
the
research
progress
of
COFs
photo/electro-catalytic
is
summarized
including
design
principles,
catalytic
performance,
reaction
mechanism.
addition,
review
also
presents
some
challenges
prospects
application
in
reduction,
laying
base
fundamental
efforts.
Advanced Materials,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Nov. 27, 2024
Abstract
Photocatalysis
leverages
solar
energy
to
overcome
the
thermodynamic
barrier,
enabling
efficient
chemical
reactions
under
mild
conditions.
It
can
greatly
reduce
reliance
on
traditional
sources
and
has
attracted
significant
research
interest.
Reticular
materials,
including
metal‐organic
frameworks
(MOFs)
covalent
organic
(COFs),
represent
a
class
of
crystalline
materials
constructed
from
molecular
building
blocks
linked
by
coordination
bonds,
respectively.
function
as
heterogeneous
catalysts,
combining
well‐defined
structures
high
tailorability
akin
homogeneous
catalysts.
In
this
review,
regulation
light
absorption,
charge
separation,
surface
in
photocatalytic
process
through
precise
molecular‐level
design
based
features
reticular
is
elaborated.
Notably,
for
MOFsmicroenvironment
modulation
around
catalytic
sites
affects
performance
delved,
with
emphasis
their
unique
dynamic
flexible
microenvironments.
For
COFs,
inherent
excitonic
effects
due
fully
nature
discussed
highlight
strategies
regulate
charge‐
and/or
energy‐transfer‐mediated
photocatalysis.
Finally,
current
challenges
future
directions
field,
aiming
provide
comprehensive
understanding
how
be
optimized
enhanced
photocatalysis
discussed.
Small,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 24, 2025
Abstract
The
photocatalytic
conversion
of
CO
2
into
products
such
as
CH
4
and
C
H
6
poses
a
significant
challenge
due
to
the
lengthy
reaction
steps
high
energy
barrier
involved.
In
this
study,
both
benzothiadiazole
(BTD)
hydroxyl
groups
(‐OH)
are
introduced
cobalt‐based
polymerized
porphyrinic
network
(PPN)
through
C‐C
coupling
reaction.
This
modification
orbital
levels
that
strengthens
ability
gain
electrons
facilitates
charge
transfer
in
PPN.
Hydroxyl
group
largely
enhances
for
light
response,
while
thiadiazole
unit
tunes
molecular
proper
level.
By
way,
BTD‐DBP‐PPN(Co)
achieves
capability
under
irradiation
light.
Co
active
site
is
reduce
facilitate
transfer.
pathway
production
has
been
studied
further
mechanism
explanation.
Overall,
series
porphyrin
centers
with
donor–acceptor
(D‐A)
structure
designed
synthesized
enhance
reduction
performance
achieve
formation
300‐W
Xe
lamp
irradiation.
