Angewandte Chemie,
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.
Accounts of Chemical Research,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 25, 2025
ConspectusCoordination
cages
formed
via
subcomponent
self-assembly
have
found
applications
in
fields
including
separation,
sensing,
catalysis,
and
the
stabilization
of
reactive
species,
due
to
their
guest
binding
abilities.
Subcomponent
self-assembly,
which
combines
dynamic
covalent
bond
(C═N)
formation
reversible
metal
coordination
(N→Metal),
has
enabled
preparation
many
intricate
polyhedral
structures
with
minimal
synthetic
effort.
This
method
been
used
prepare
multitopic
pyridyl-imine
ligands
that
form
edges
or
faces
polyhedra,
octahedral
ions,
FeII,
CoII,
ZnII,
defining
vertices.
The
use
CuI
is
less
widely
reported,
as
tetrahedral
geometry
requires
only
two
bidentate
ligands,
can
lead
lower-nuclearity
assemblies
instead
three-dimensional
cages.
flexibility
also
adds
a
challenge
fabrication
well-defined
nanostructures.
Account
summarizes
series
higher-order
CuI-based
design
principles
derived
from
syntheses.
Starting
development
challenges
preparing
cages,
we
discuss
circumvention
oligomer
control
process
through
(i)
ligand
engineering,
(ii)
vertex
design,
(iii)
guest-induced
structural
transformations.
Aromatic
stacking
between
corranulene-containing
exploited
produce
5-fold
interlocked
[2]catenane,
whereas
incorporation
sterically
hindered
triptycene
minimizes
aromatic
produces
double-octahedron
hexagonal
prism.
These
illustrate
importance
engineering
for
obtaining
complex
structures.
We
explored
homo-
heterobimetallic
vertices
distinct
strategies.
First,
dicopper(I)
helicates
were
employed
cage
vertices,
second,
subcomponents
nonconverging
vectors
used.
Such
bimetallic
are
challenging
incorporate
when
templates
used,
but
renders
them
accessible.
closed-shell
electronic
configuration
endow
photoluminescence,
providing
circularly
polarized
luminescence
presence
helicity-enriched
flexible
sphere
facilitates
transformations
upon
addition
suitable
guests.
One
such
system
able
self-sort
express
most
thermodynamically
stable
host–guest
undergo
changes
response
different
temperatures
solvents.
insights
gained
about
bases
these
may
help
enable
other
novel
nanostructures
functions
usefully
differ
exclusively
centers.
Abstract
Metal‐organic
cages
(MOCs)
are
a
class
of
compounds
formed
through
the
coordination
metal
ions
with
organic
ligands
to
create
well‐defined
and
cage‐like
structure.
These
unique
structures
offer
versatile
environments
for
catalyzing
wide
range
chemical
reactions.
The
catalytic
capabilities
MOCs
significantly
influenced
by
nature
ions,
functional
ligands,
cage
Notably,
confined
spaces
within
can
lead
enhanced
reaction
efficiencies,
particularly
in
processes
such
as
light‐induced
hydrogen
generation
photocatalytic
reduction
CO₂.
Furthermore,
show
great
potential
photo‐organic
synthesis
due
structure,
which
provides
environment
allows
encapsulating
molecules,
making
them
useful
improving
selectivity
efficiency
process.
This
review
reports
development
photocatalysis,
focusing
on
structural
design
regulation
strategy
build
production,
CO
2
reduction,
transformation.
Insights
into
photocatalysis
discussed
including
challenges
further
research
direction
MOC‐based
photocatalysis.
Inorganic Chemistry Frontiers,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
This
article
presents
the
influence
of
lanthanide
size
and
ligands
conformational
flexibility
on
assemblies
their
corresponding
luminescent
properties.
ACS Omega,
Год журнала:
2025,
Номер
10(10), С. 9890 - 9902
Опубликована: Март 3, 2025
Metal-Organic
Frameworks
(MOFs),
as
a
new
type
of
porous
material,
have
attracted
widespread
attention
in
the
fields
chemistry,
materials
science,
and
biomedicine
owing
to
their
unique
structural
characteristics
potential
for
functionalization.
This
review
summarizes
latest
research
progress
MOFs
field
steroid
compounds,
including
purification
separation
steroids,
sensing
detection,
catalytic
transformation,
drug
delivery.
First,
we
explore
how
structure
chemical
functionalization
achieve
efficient
compounds.
Second,
high
sensitivity
selectivity
well
application
actual
sample
analysis,
are
analyzed.
Furthermore,
role
transformation
reactions
is
discussed,
performance
catalysts
or
catalyst
carriers.
Finally,
focus
on
innovative
applications
delivery
systems,
especially
advantages
controlled
release
targeted
article
also
explores
future
development
trends
prospects
highlighting
challenges
opportunities
material
design,
strategies,
practical
implementations.
Through
this
review,
aim
provide
comprehensive
theoretical
basis
guidance
further
steroids.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 24, 2025
We
report
an
efficient
one-pot
aqueous
synthesis
of
ring-in-rings
complexes
featuring
customizable
π-stacked
dyads.
Conventional
methods
for
such
often
suffer
from
poor
solubility
and
low
yields
due
to
irreversible
kinetically
controlled
reactions.
To
overcome
these
limitations,
we
developed
a
strategy
combining
noncovalent
preassembly
with
dynamic
covalent
bonding
secure
complex
as
the
exclusive
thermodynamic
product.
Through
complexation
cucurbit[8]uril
(CB[8]),
folded
conformation
was
induced
in
aldehyde-functionalized
bis(phenylpyridinium)
derivative,
predisposing
reactive
aldehyde
groups
promote
acylhydrazone
condensation
aromatic
dihydrazides.
The
method
achieves
high
conversion
purity,
enabling
direct
single-crystal
growth
without
need
purification.
successfully
synthesized
dyads
across
diverse
moieties,
including
five
distinct
structures
demonstrating
dimeric
cofacial
stacking.
Kinetic
analysis
reveals
that
CB[8]
increases
ceiling
temperature
reaction,
rendering
process
both
thermodynamically
favorable.
modular
nature
this
allows
precise
tuning
photophysical
properties
by
simply
altering
linker
lengths
central
cores,
providing
facile
platform
exploring
structure-function
relationships
beyond.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Май 16, 2025
Although
discrete
self-assembled
cage
compounds
with
single-metal
centers
mimicking
natural
bioreactors
for
catalysis
have
been
extensively
investigated,
studies
on
those
multimetal
active
centers,
i.e.,
cluster
(CACs),
less
explored.
Herein,
we
present
the
design
and
synthesis
of
a
novel
cluster-based
supramolecular
reaction
pump
(CSRP-1)
featuring
four
CACs
that
facilitate
catalysis.
CSRP-1
holds
cationic
tetrahedral
structure,
comprising
WS3Cu3
clusters,
each
positioned
at
one
vertex
interconnected
by
dipyridyl
linkers.
Substrates,
including
aryl
iodides
or
primary
secondary
amines,
enter
cavity
replacing
N,N-dimethylformamide
through
weak
Cu···I/N
interactions.
This
leverages
coordinatively
unsaturated
Cu
within
CAC
to
activate
substrates,
resulting
in
efficient
catalytic
amination.
works
like
dynamic
pump,
upon
completion
reaction,
amine
product
is
expelled
from
cavity,
allowing
cycle
repeat
maintained
efficiency.
Theoretical
calculations
complement
experimental
findings,
providing
key
insights
into
mechanism
synergistic
role
clusters
work
offers
new
paradigm
broad
applicability
various
organic
reactions.
Nature Communications,
Год журнала:
2025,
Номер
16(1)
Опубликована: Май 22, 2025
Selection
of
a
suitable
species
from
dynamic
library
in
response
to
external
stimuli
is
key
event
evolution,
adaptation,
and
switching.
The
desymmetrization
building
blocks
enables
the
generation
configurational
isomers
for
self-assembly,
which
rational
approach
creating
complicated
without
increasing
variety
components.
However,
because
their
structural
similarity,
selection
such
challenging.
Here
we
show
an
artificial
molecular
system
two
types
self-assemblies
are
separately
selected
consisting
16
hexameric
cube-shaped
entities
assembled
CS-symmetric
gear-shaped
amphiphiles
upon
binding
or
three
guest
molecules.
were
not
only
by
induced-fit
caused
molecules
but
also
induction
spatial
arrangements
cluster
assemblies.
These
results
indicate
that
mutual
multivariant
optimization
hidden
strategy
create
order
chaos
systems.
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.
