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.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(23), С. 15787 - 15795
Опубликована: Май 13, 2024
The
encapsulation
of
different
guest
molecules
by
their
recognition
domains
proteins
leads
to
selective
binding,
catalysis,
and
transportation.
Synthetic
hosts
capable
selectively
binding
guests
in
cavities
mimic
the
function
are
highly
desirable
but
challenging.
Here,
we
report
three
ladder-shaped,
triple-cavity
metallacages
prepared
multicomponent
coordination-driven
self-assembly.
Interestingly,
porphyrin-based
metallacage
is
heteroleptic
fullerenes
(C60
or
C70)
coronene
using
its
cavities,
allowing
distinct
allosteric
upon
addition
C60
C70.
Owing
affinities
one
molecule
central
cavity
two
units
side
while
encapsulating
C70
cavity.
rational
design
multicavity
assemblies
that
enable
will
guide
further
advanced
supramolecular
constructs
with
tunable
properties.
Chemistry - A European Journal,
Год журнала:
2024,
Номер
30(43)
Опубликована: Май 29, 2024
Abstract
Metal‐organic
frameworks
(MOFs)
and
metal‐organic
cages
(MOCs)
have
garnered
significant
attention
as
promising
photocatalysts
due
to
their
tunable
chemical
structures
integrated
multifunctionality.
To
increase
the
photocatalytic
efficiency,
strategies
like
ligand
functionalization,
introducing
additional
catalytic
sites,
doping
or
encapsulating
photosensitizers
been
explored
for
both
MOFs
MOCs.
This
concept
review
focuses
on
recent
advancements
in
utilizing
MOCs
hydrogen
production,
highlighting
unique
characteristics
respective
mechanisms
this
field.
Moreover,
it
outlines
current
challenges
prospects
faced
by
MOCs,
offering
an
outlook
future
domain.
The
conversion
of
toluene
into
high-value
products
without
generating
undesired
CO2
remains
a
critical
challenge.
Selective
oxidation
under
visible
light
irradiation
has
emerged
as
promising
solution.
This
review
offers
comprehensive
interpretation
photocatalytic
transformations
in
heterogeneous
oxidation.
We
start
by
outlining
the
basic
mechanism
C–H
bond
activation
and
provide
an
overview
reactive
oxygen
species
(ROS)
within
systems.
Subsequently,
we
summary
strategies
that
have
been
developed
to
enhance
selectivity
system.
Following
this,
advanced
characterization
techniques
density
functional
theory
(DFT)
calculations
are
discussed
for
understanding
structure-performance
relationship
photocatalysts
mechanisms
underlying
processes.
Finally,
put
forward
detailed
discussion
current
challenges
potential
directions
future
research,
with
aim
offering
valuable
insights
this
emerging
field.
believe
will
not
only
spark
greater
creativity
optimizing
but
also
offer
designing
other
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 11, 2025
The
electrocatalytic
oxidation
of
benzyl
alcohol
to
benzoic
acid
is
a
process
that
often
requires
high
voltage,
leading
increased
energy
consumption,
side
reactions
(oxygen
evolution
reaction
(OER)),
and
catalyst
degradation.
Herein,
our
study
introduces
novel
approach.
We
demonstrate
PtZn-ZnOx
featuring
PtZn
intermetallic
structure
with
abundant
interfaces
on
the
surface
allows
for
an
impressive
selectivity
99.5%
at
low
potential
0.725
V
(vs
reversible
hydrogen
electrode,
RHE),
which
0.6
lower
than
most
reported
studies.
This
testament
efficiency
catalyst,
as
it
significantly
reduces
occurrence
reactions,
more
efficient
sustainable
process.
experimental
density
functional
theory
calculations
demonstrated
adsorption
Ph–CH2OH
Ph–CHO
generation
electrophilic
OH*
were
promoted
due
unsaturated
coordination
Zn
atom
in
interfaces.
Furthermore,
potential-determining
step
coupling
was
barrier
interface,
improved
catalytic
activity
selectivity.
outlines
approach
designing
highly
electrocatalysts
high-efficiency
valorization
voltages.
Inorganic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 12, 2025
Coordination
cages
with
specific
properties
and
functionalities
are
utilized
as
reaction
vessels
for
the
desired
chemical
transformation
of
substrates.
The
symmetry
inherent
cavity
coordination
can
influence
host–guest
interactions
outcome
in
their
confined
space.
However,
impact
cage
shape
on
different
transformations
remains
unclear.
In
this
chapter,
we
report
chemo-selective
anthracene
derivative
using
three
geometrically
distinct
Pd6
(CC2,
CC3,
CC4).
Photoirradiation
9-bromoanthracene
(G3)
distorted
double-square
(CC2)
yields
anthracene-9,10-dione,
while
known
(CC3)
forms
a
[4
+
4]
cycloaddition
product.
same
bowl-shaped
(CC4)
resulted
oxidized
Through
combination
experimental
computational
studies,
demonstrate
that
size
significantly
pathways
encapsulated
derivative,
leading
to
chemo-selectivity.
Furthermore,
observe
encapsulation
cavities
(CC2
CC4)
leads
significant
enhancement
rate
photooxidation
G3.
This
work
underscores
versatility
water-soluble
synthetic
chemistry,
offering
interesting
avenues
transformation.
Accounts of Chemical Research,
Год журнала:
2025,
Номер
unknown
Опубликована: Май 2, 2025
ConspectusIn
recent
years,
multicomponent
self-assembly
has
emerged
as
a
pivotal
strategy
in
supramolecular
chemistry,
enabling
the
construction
of
artificial
systems
with
enhanced
functionalities
that
surpass
those
individual
molecular
components.
These
assemblies
have
garnered
significant
interest
due
to
their
potential
applications
recognition,
catalysis,
and
biomedical
engineering.
However,
achieving
precise
control
over
assembly
process
remains
challenge,
increased
structural
complexity
often
results
thermodynamic
mixtures,
limiting
practical
applications.
In
this
context,
metal-coordination-driven
promising
strategy,
moderate
strength
good
directionality
metal-ligand
bonds
ensure
formation
discrete
architectures
well-defined
structures
geometries.
Notably,
integration
pyridyl
carboxylate
donors
cis-Pt(II)
nodes
offers
an
effective
approach
for
constructing
metallacages.
This
method
is
particularly
attractive
its
ability
enable
heteroleptic
assembly,
along
accessibility
tunability
ligands,
which
impart
desirable
photophysical
properties
anticancer
activities.This
Account
provides
comprehensive
overview
our
work
on
design,
preparation,
functionalization
metallacages
via
ligands
nodes.
By
strategically
tailoring
ligand
adjusting
number
coordination
sites,
we
successfully
constructed
diverse
geometries,
including
tetragonal
hexagonal
prisms,
triple-cavity
ladders,
truncated
octahedra,
cyclic
bis[2]catenanes,
etc.
particular,
highlight
use
functional
such
tetraphenylethylene,
hexaphenylbenzene,
perylene
diimide,
porphyrin
derivatives,
explore
these
Tetraphenylethylene
hexaphenylbenzene
derivatives
are
propeller-shaped
molecules
aggregation-induced
emission
properties,
enhancing
both
solution
solid
state.
Perylene
diimide
electron-deficient,
planar
conjugated
structures,
contribute
strong
solution,
thereby
improving
host-guest
chemistry
luminescent
Porphyrin
owing
excellent
photosensitivity,
endow
photocatalytic
capabilities.
Additionally,
other
phenanthroline
triazine
been
employed
antibacterial
SO2
adsorption
respectively,
Furthermore,
metallacage-cross-linked
networks
exhibit
mechanical
superior
processability,
making
them
candidates
materials.
At
conclusion
Account,
address
challenges
future
perspectives
development
We
believe
ongoing
research
field
will
significantly
advance
understanding
metal-coordination
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(45), С. 30933 - 30946
Опубликована: Окт. 21, 2024
Flavin
adenine
dinucleotide
(FAD),
serving
as
a
light-absorbing
coenzyme
factor,
can
undergo
conformationally
isomeric
complexation
within
different
enzymes
to
form
various
enzyme-coenzyme
complexes,
which
exhibit
photocatalytic
functions
that
play
crucial
role
in
physiological
processes.
Constructing
an
artificial
photofunctional
system
using
FAD
or
its
derivatives
not
only
develop
biocompatible
systems
with
excellent
activities
but
also
further
enhance
our
understanding
of
the
biological
systems.
Here,
we
demonstrate
supramolecular
approach
for
constructing
enzyme-coenzyme-type
host-guest
complex
photoinduced
catalytic
function
water.
First,
have
designed
and
synthesized
water-soluble
tetraphenylethene
(TPE)-based
octacationic
molecular
cage
(