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.
Accounts of Chemical Research,
Год журнала:
2024,
Номер
57(22), С. 3277 - 3291
Опубликована: Окт. 9, 2024
ConspectusThe
emulation
of
ingenious
biofunctions
has
been
a
research
focus
for
several
decades.
Metal-organic
cages
(MOCs),
as
type
discrete
supramolecular
assembly
with
well-defined
shapes
and
cavities,
have
aroused
great
interest
in
chemists
to
imitate
natural
protein
or
enzymes.
However,
genuinely
achieve
tailored
functionalities
reactivities
enzymes,
the
design
cage
structures
combining
both
confined
microenvironment
active
site
is
prerequisite.
Therefore,
integration
functionalized
motifs
into
MOCs
expected
provide
feasible
approach
construct
biofunctional
nanospaces,
which
not
only
allows
modulation
properties
applications
such
molecular
recognition,
transport,
catalysis
but
also
creates
unique
microenvironments
that
promote
enzymatic
effects
special
selectivities,
thereby
providing
versatile
platform
exceptional
biomimetic
functions
beyond.In
this
Account,
we
specifically
on
our
toward
engineering
confined-nanospaces
via
incorporation
M(ImPhen)
ACS Catalysis,
Год журнала:
2024,
Номер
14(17), С. 12793 - 12805
Опубликована: Авг. 9, 2024
The
realm
of
catalytic
chemistry
has
witnessed
notable
advancements
through
the
integration
photoredox
confined
synergistic
catalysis,
a
method
that
synergizes
benefits
and
catalysis.
This
innovative
approach
facilitates
generation
reactive
intermediates
via
reactions,
while
microenvironment
tailors
distinct
selectivity
processes.
Despite
its
progress,
several
aspects,
including
intricacies
encapsulation
process,
characteristics
underlying
mechanisms,
remain
to
be
fully
elucidated.
In
order
answer
these
questions,
this
work
investigated
1,3-rearrangement
reaction
mechanism
cinnamyl
ammonium
bromide
within
metallocage
(K12[Ga4L6],
L
=
N,N′-bis(2,3-dihydroxybenzoyl)-1,5-diaminonaphthalene).
Through
molecular
dynamics
simulations,
process
was
meticulously
analyzed
determine
initial
host–guest
assembly
structure.
Subsequent
quantum
chemical
calculations
shed
light
on
mechanistic
details
nuances
1,3-rearrangement.
investigation
reveals
radical
unfolds
in
two
pivotal
stages:
breaking
C–N
bond,
accompanied
by
an
electronic
state
conversion
facilitated
formation
conducted
space
metallocage.
Notably,
catalysis
plays
crucial
role
altering
product
selectivity,
demonstrating
potential
strategy
guide
pathways
with
enhanced
precision.
study
not
only
clarifies
operational
but
also
lays
foundation
for
future
innovations
highlighting
critical
factors
influence
efficiency.
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.
Organic Chemistry Frontiers,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
We
present
two
protocols
for
the
efficient
synthesis
of
substituted
1-naphthols.
DFT
calculations
and
verification
experiments
elucidate
mechanism.
Scale-up
product
conversion
confirm
reaction's
practical
potential.
Chinese Journal of Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 19, 2025
Comprehensive
Summary
The
preparation
and
resolution
of
chiral
molecules
hold
significant
importance
in
scientific
industrial
domains,
such
as
drug
development
manufacturing.
In
recent
years,
porous
frameworks
have
attracted
increasing
attention
asymmetric
catalysis
enantiomer
due
to
their
excellent
performance.
metal‐organic
(MOFs),
covalent
organic
(COFs),
cages
(POCs),
coordination
(PCCs)
are
important
representative
the
framework
family.
Significantly,
chirality
can
be
easily
introduced
into
these
materials
through
simple
bottom‐up
or
post‐modification
methods,
thereby
promoting
applications
related
chirality.
this
review,
we
systematically
summarize
synthesis
strategies
four
classes
enantiomeric
resolution.
Finally,
present
some
perspectives
on
future
frameworks.
Key
Scientists
Significant
progress
has
been
made
frameworks,
primarily
driven
by
application
molecules.
This
area
research
seen
contributions
from
many
distinguished
scientists.
A
particularly
milestone
was
reached
2000,
when
Kimoon
Kim
reported
first
catalytic
Chiral
Metal‐Organic
Framework
(CMOF).
2001,
Lin
et
al
.
a
new
generation
recyclable
CMOF
capable
separation
heterogeneous
catalysis.
Simultaneously,
researchers
Cui
Duan
substantial
contributions,
advancing
field
considerably.
Furthermore,
notable
developments
Covalent
Organic
Frameworks
(CCOFs),
with
pioneering
work
like
Jiang,
Wang,
Cui.
Meanwhile,
groups
Su
Li
strides
cages.
These
remarkable
accomplishments
drawn
considerable
interest.
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.
