Compared
to
bulk
solvents,
reactions
in
the
confined
spaces
of
supramolecular
self-assemblies
feature
rate
acceleration,
high
efficiency
and
substrate
selectivity.
These
advantages
lead
efficient
catalytic
excellent
selectivity
enantioselective
photochemical
transformations.
During
last
few
years,
photocatalysis
has
developed
into
one
most
powerful
strategies
construct
enantioenriched
chiral
compounds.
In
this
review,
recent
advances
taking
place
within
assemblies
are
summarized,
with
an
emphasis
on
specific
modes
chemical
Organization
data
follows
a
subdivision
according
host
reaction
type.
At
last,
current
limitations
future
research
orientation
field
discussed.
Abstract
Covalent
Organic
Frameworks
(COFs)
have
emerged
as
promising
platforms
for
photocatalytic
synthesis
of
hydrogen
peroxide
(H
2
O
)
due
to
their
tunable
chemical
compositions
and
efficient
catalytic
functionalities.
Inspired
by
the
role
microenvironment
in
enzyme
catalysis,
this
study
introduces
various
N‐heterocyclic
species
into
β
‐ketoenamine
COFs
(N
x
‐COFs,
where
N
represents
number
nitrogen
atoms
N‐heterocycle)
regulate
around
sites
on
acceptor‐donor‐acceptor
(A‐D‐A)
foroverall
H
photosynthesis
pure
water.
The
‐COFs
exhibit
distinct
photosynthetic
rates
following
sequence
3
‐COF
>
1
0
‐COF,
with
triazine
structure
showing
highest
generation
rate
(4881
µmol
h
−1
g
decent
solar‐to‐chemical
conversion
(SCC)
efficiency
(0.413%),
surpassing
many
existing
COF‐based
catalysts.
In
situ
characterization
theoretical
calculations
support
experimental
results,
revealing
that
promote
through
both
an
indirect
stepwise
single‐electron
oxygen
reduction
reaction
(1e
−
ORR)
mechanism
a
direct
two‐electron
water
oxidation
(2e
WOR)
pathway.
This
advances
design
paradigm
photocatalysts
modulating
within
A‐D‐A
COFs,
paving
way
development
more
robust
systems
overall
.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 8, 2025
Enzymatic
catalysis
in
biological
systems
is
characterized
by
the
specific
pocket
confinement
imposed
various
protein
matrixes,
enabling
synthesis
of
a
diverse
array
functional
biomolecules.
Development
new
catalysts
that
incorporate
multiple
catalytic
centers
within
enzyme-mimic
confined
spaces
presents
meaningful
yet
challenging
project
for
synthetic
chemists.
Here,
we
present
our
recent
achievement
synthesizing
chiral
photosensitive
metal-organic
cage
(cPMOC),
Δ4-/Λ4-MOC-68-Ru4,
which
possesses
pockets
can
facilitate
visible-light-induced
asymmetric
cascade
intermolecular
[2
+
2]
cycloaddition/acyloin
rearrangement
first
time.
The
current
photochemical
transformation
affords
bicyclo[3.2.1]octanes
with
opposite
regiospecificity
contrast
to
well-established
thermodynamically
favored
[3
cycloaddition
transformations
similar
reaction
counterparts.
distinctive
size
2
inhibits
dimerization
α,β-unsaturated
ketones
and
promotes
heterocycloaddition
between
ketone
smaller
cyclic
1,2-dione,
underscoring
critical
role
microenvironmental
shape
guest
binding
determining
reactivity.
Molecules,
Год журнала:
2025,
Номер
30(8), С. 1680 - 1680
Опубликована: Апрель 9, 2025
Photocatalysis
is
a
key
strategy
for
the
development
of
sustainable
solar-driven
chemical
processes.
In
this
work,
we
report
synthesis
and
characterization
novel
organometallo-ionosilica
material
derived
from
self-condensation
an
alcoxysilane
functionalized
Ir(III)
complex.
acetonitrile
suspension,
retains
photophysical
properties
its
precursor
in
solution
same
solvent,
together
with
significant
absorption
visible
between
400
500
nm.
As
heterogeneous
photocatalyst,
showed
high
efficiency
reductive
dehalogenation
2-bromoacetophenone
under
blue
light
irradiation,
achieving
yields
conversion
about
90%,
excellent
recyclability
seven
catalytic
cycles,
retaining
more
than
70%
efficiency.
All
these
self-condensed
highlight
potential
as
efficient
photocatalyst
applications
organic
redox
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(36)
Опубликована: Июнь 14, 2024
Polyradical
cages
are
of
great
interest
because
they
show
very
fascinating
physical
and
chemical
properties,
but
many
challenges
remain,
especially
for
their
synthesis
characterization.
Herein,
we
present
the
a
polyradical
cation
cage
1
Chemistry - A European Journal,
Год журнала:
2024,
Номер
unknown
Опубликована: Июль 22, 2024
Abstract
In
the
realm
of
solar
energy
utilization,
there
is
a
growing
focus
on
designing
and
implementing
effective
photocatalytic
systems,
for
conversion
into
valuable
chemical
fuels.
The
potential
Covalent
Organic
Polymers
(COPs)
as
photocatalysts
visible‐light‐driven
organic
transformation
has
been
widely
investigated,
positioning
them
promising
candidates
in
this
field.
design
COPs,
introducing
donor‐acceptor
arrangement
facilitates
transfer
electrons
from
donor
to
acceptor,
creating
charge
complex
leading
enhanced
conductivity
improved
separation.
Here
we
present
novel
hydrazone‐linked
covalent
polymer
ETBC‐PyHz
containing
TPE
pyridine
acceptor.
Utilizing
this,
an
efficient
method
developed
oxidative
cross‐coupling
reaction
involving
C−S
bond
formation.
This
process
involves
arylhydrazines
arenethiols,
results
production
unsymmetrical
diaryl
sulfides
via
formation
aryl
thioarene
radicals.
holds
significant
importance
because
byproducts
produced
during
are
nitrogen
water,
making
it
environmentally
benign.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
unknown
Опубликована: Сен. 24, 2024
Sustainable
electricity-to-chemical
conversion
via
the
utilization
of
artificial
catalysts
inspired
by
redox
biological
systems
holds
great
significance
for
catalyzing
synthesis.
Herein,
we
develop
a
biomimetic
electrosynthesis
strategy
mediated
nicotinamide
adenine
dinucleotide
(NADH)
mimic-containing
coordination
capsule
efficiently
producing
α-hydroxy/amino
esters.
The
saturated
metal
centers
worked
as
an
electron
relay
to
consecutively
accept
single
electrons
while
donating
two
NAD
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 6, 2024
Abstract
An
enzyme‐mimicking
catalytic
system
has
been
established
using
a
singular
palladium‐based
octahedral
cage
as
the
supramolecular
reactor,
deftly
unlocking
off‐on‐off
selectivity
in
semi‐hydrogenation
of
alkynes.
Water
serves
critical
regulator,
modulating
catalyst
states,
reaction
rates,
and
endpoints.
The
choice
solvent
influences
activity
host–guest
binding
types
homogeneous
heterogeneous
catalysis,
effectively
modifying
steps
involved
Z
→
E
isomerization
during
Kinetic
inhibition
experiments
indicate
that
mimics
activation
characteristics
enzymes
towards
substrates,
enabling
selective
transformations
within
confined
environment.
utility
this
switchable
cage‐confined
catalysis
demonstrated
synthesis
modification
complex
biologically
active
molecules
with
controllable
/
selectivity.
This
work
sheds
light
on
design
control
artificial
counterparts
enzymes,
offering
fundamental
insights
into
factors
influencing
biological
macromolecules.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(29), С. 20414 - 20424
Опубликована: Июль 10, 2024
The
structural
dynamics
of
artificial
assemblies,
in
aspects
such
as
molecular
recognition
and
transformation,
provide
us
with
a
blueprint
to
achieve
bioinspired
applications.
Here,
we
describe
the
assembly
redox-switchable
chiral
metal-organic
cages
Λ
