Journal of the American Chemical Society,
Год журнала:
2021,
Номер
143(4), С. 2123 - 2129
Опубликована: Янв. 22, 2021
The
construction
of
three-dimensional
covalent
organic
frameworks
(3D
COFs)
has
proven
to
be
very
challenging,
as
their
synthetic
driving
force
mainly
comes
from
the
formation
bonds.
To
facilitate
synthesis,
rigid
building
blocks
are
always
first
choice
for
designing
3D
COFs.
In
principle,
it
should
appealing
construct
COFs
flexible
blocks,
but
there
some
obstacles
blocking
development
such
systems,
especially
designed
synthesis
and
structure
determination.
Herein,
we
reported
a
novel
highly
crystalline
COF
(FCOF-5)
with
C–O
single
bonds
in
block
backbone.
By
merging
17
continuous
rotation
electron
diffraction
data
sets,
successfully
determined
crystal
FCOF-5
6-fold
interpenetrated
pts
topology.
Interestingly,
is
can
undergo
reversible
expansion/contraction
upon
vapor
adsorption/desorption,
indicating
breathing
motion.
Moreover,
smart
soft
polymer
composite
film
was
fabricated,
which
show
vapor-triggered
shape
transformation.
Therefore,
constructed
exhibit
interesting
behavior,
finally,
totally
new
type
porous
crystals
made
pure
framework
announced.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(34)
Опубликована: Апрель 24, 2023
Abstract
Intensifying
energy
crises
and
severe
environmental
issues
have
led
to
the
discovery
of
renewable
sources,
sustainable
conversion,
storage
technologies.
Photocatalysis
is
a
green
technology
that
converts
eco‐friendly
solar
into
high‐energy
chemicals.
Covalent
organic
frameworks
(COFs)
are
porous
materials
constructed
by
covalent
bonds
show
promising
potential
for
converting
chemicals
owing
their
pre‐designable
structures,
high
crystallinity,
porosity.
Herein,
we
highlight
recent
progress
in
synthesis
COF‐based
photocatalysts
applications
water
splitting,
CO
2
reduction,
H
O
production.
The
challenges
future
opportunities
rational
design
COFs
advanced
discussed.
This
Review
expected
promote
further
development
toward
photocatalysis.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(27), С. 12390 - 12399
Опубликована: Июнь 29, 2022
The
reaction
of
5,5′-([2,2′-bipyridine]-5,5′-diyl)diisophthalaldehyde
(BPDDP)
with
cyclohexanediamine
and
[benzidine
(BZ)/[2,2′-bipyridine]-5,5′-diamine
(BPDA)],
respectively,
affords
a
nitrogen-rich
porous
organic
cage
BPPOC
two
two-dimensional
(2D)
covalent
frameworks
(COFs),
USTB-1
USTB-2
(USTB
=
University
Science
Technology
Beijing),
under
suitable
conditions.
Interestingly,
single-crystal
X-ray
diffraction
structure
is
able
to
successfully
transform
into
(newly
converted
COFs
denoted
as
USTB-1c
USTB-2c,
respectively)
upon
exchange
the
imine
unit
in
by
BZ
BPDA.
Such
transformation
also
enables
isolation
analogous
(USTB-3c
USTB-4c)
on
basis
an
isostructural
cage,
BTPOC,
which
derived
from
5,5′-([2,2′-bithiophene]-4,4′-diyl)diisophthalaldehyde
(BTDDP)
cyclohexanediamine.
However,
conventional
solvothermal
between
BTDDP
BPDA
leads
impure
phase
USTB-4
containing
incompletely
aldehyde
groups
due
limited
solubility
building
block.
newly
prepared
have
been
characterized
nuclear
magnetic
resonance
spectroscopy,
Fourier
infrared
scanning
electron
microscopy,
transmission
microscopy.
In
particular,
absorb
iodine
vapor
uptake
5.64
g
g–1,
breaking
cage's
(POC's)
record
value
3.78
g–1.
Nevertheless,
cage-derived
exhibit
improved
adsorption
capability
comparison
directly
synthesized
counterparts,
highest
5.80
g–1
for
USTB-1c.
mechanism
investigation
unveils
superiority
nitrogen
atoms
sulfur
POCs
capture
assistance
definite
crystal
structures.
This,
combination
porosity,
synergistically
influences
capacity
COFs.
Journal of the American Chemical Society,
Год журнала:
2021,
Номер
143(4), С. 2123 - 2129
Опубликована: Янв. 22, 2021
The
construction
of
three-dimensional
covalent
organic
frameworks
(3D
COFs)
has
proven
to
be
very
challenging,
as
their
synthetic
driving
force
mainly
comes
from
the
formation
bonds.
To
facilitate
synthesis,
rigid
building
blocks
are
always
first
choice
for
designing
3D
COFs.
In
principle,
it
should
appealing
construct
COFs
flexible
blocks,
but
there
some
obstacles
blocking
development
such
systems,
especially
designed
synthesis
and
structure
determination.
Herein,
we
reported
a
novel
highly
crystalline
COF
(FCOF-5)
with
C–O
single
bonds
in
block
backbone.
By
merging
17
continuous
rotation
electron
diffraction
data
sets,
successfully
determined
crystal
FCOF-5
6-fold
interpenetrated
pts
topology.
Interestingly,
is
can
undergo
reversible
expansion/contraction
upon
vapor
adsorption/desorption,
indicating
breathing
motion.
Moreover,
smart
soft
polymer
composite
film
was
fabricated,
which
show
vapor-triggered
shape
transformation.
Therefore,
constructed
exhibit
interesting
behavior,
finally,
totally
new
type
porous
crystals
made
pure
framework
announced.
