Advanced Functional Materials,
Год журнала:
2024,
Номер
35(3)
Опубликована: Сен. 20, 2024
Abstract
Chiral
metallacages,
with
their
precisely
distributed
luminescent
and
chiral
units
inherent
adaptive
chirality,
represent
an
ideal
framework
for
developing
circularly
polarized
luminescence
(CPL)‐active
materials.
Despite
potential,
enhancing
the
dissymmetry
factor
(
g
lum
)
of
metallacage‐based
materials
remains
a
significant
challenge.
In
this
study,
useful
approach
is
proposed
by
co‐assembling
donor
metallacage
Δ
4
/
Λ
‐Zn
A
achiral
acceptor
Nile
red
(NiR),
achieving
efficient
energy
chirality
transfer
resulting
in
enhanced
CPL
these
co‐assemblies.
More
importantly,
microfluidic
laminar
flow
utilized,
known
providing
stable
driving
forces
confined
spaces,
to
achieve
marked
improvement
values
co‐assemblies
within
polymethyl
methacrylate
(PMMA)
films.
Computational
fluid
dynamics
(CFD)
simulations
small‐angle
X‐ray
scattering
(SAXS)
experiments
confirm
that
films
containing
/NiR,
prepared
via
chips,
display
well‐defined
distributions
metallacages
NiR
due
controllable
assembly
process
facilitated
flow.
This
work
pioneers
new
methodology
significantly
enhance
materials,
opening
avenues
field
photonics.
Metal–organic
cycles/cages
(MOCs)
are
a
class
of
nanoscale
molecular
entities
that
possess
distinct
shapes
and
sizes
designed
synthesized
through
the
predictable
integration
organic
inorganic
ligands.
The
diverse
functionalities
MOCs
render
them
valuable
in
fields
biology,
chemistry,
materials.
First,
cavity
renders
suitable
for
host–guest
interactions,
which
subsequently
employed
to
induce
conformational
changes,
this
approach
is
particularly
advantageous
catalysis,
sensing,
controlled
loading
release.
Furthermore,
MOC-
polymer-based
aggregates
can
be
applied
biomedical
research
cascaded
light-harvesting
systems.
Benefiting
from
high
specific
surface
area,
initial
exploration
MOC-based
hierarchical
assemblies
indicates
their
potential
applications
biomedicine
catalysis.
microsheets
centimeter
films
used
dual-mode
catalysis
novel
wound
dressing
nonhealing
wounds.
In
addition,
design
synthesis
with
different
various
strategies
discussed.
We
summarized
latest
progress
past
5
years
Review.
Angewandte Chemie,
Год журнала:
2024,
Номер
136(50)
Опубликована: Авг. 20, 2024
Abstract
The
dynamic
behaviour
of
metal‐ligand
bonding
cultivates
stimuli‐mediated
structural
transformations
in
self‐assembled
molecular
architectures.
propensity
synthetically
designed
systems
to
interchange
between
higher‐order
architectures
is
increased
multi‐fold
when
the
building
blocks
have
higher
conformational
degrees
freedom.
Herein,
we
report
a
new
ligand,
(2,7‐bis(di(pyridin‐4‐yl)amino)‐9
H
‐fluoren‐9‐one)
(
L
),
which,
upon
self‐assembly
with
cis
‐[(ethylene‐1,2‐diamine)Pd(NO
3
)
2
]
acceptor
M
resulted
formation
6
trifacial
barrel
C1
water.
Interestingly,
during
crystallization,
rare
12
triangular
orthobicupola
architecture
C2
was
generated
along
.
could
also
be
solution
via
application
several
stimuli.
aqueous
media
stabilize
one
trans
‐stilbene
tS
or
cS
molecule
its
cavity,
selectivity
for
former
from
their
mixture.
Moreover,
acted
as
an
effective
host
prevent
otherwise
facile
photoisomerization
inside
hydrophobic
cavity
under
UV
irradiation.
Conversely,
visible‐light‐induced
reverse
isomerization
encapsulated
achieved
readily
due
better
stabilization
within
and
transparency
visible
light.
A
multi‐functional
system
therefore
designed,
which
at
same
time
stimuli‐responsive,
shows
isomer
selectivity,
photo‐protects
‐stilbene.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
unknown
Опубликована: Сен. 30, 2024
Host-guest
dynamic
systems
in
coordination-driven
metallo-organic
cages
have
gained
significant
attentions
since
their
promising
applications
chiral
separation,
drug
delivery,
and
catalytical
fields.
To
maximize
guest-binding
affinity,
hosts
adopting
multiple
conformations
are
widely
investigated
on
structural
flexibility
for
guest
accommodation.
In
this
study,
a
novel
cage
S
with
breathing
inner
cavity
freely
twisted
side
chains
was
proposed.
Single-crystal
X-ray
diffraction
analyses
depicted
characteristic
"breathing-helical"
system
the
semiflexible
framework,
which
led
to
an
unprecedent
co-crystallisation
of
racemic
symmetric
via
encapsulation
locking
C
Angewandte Chemie,
Год журнала:
2024,
Номер
unknown
Опубликована: Сен. 30, 2024
Abstract
Host‐guest
dynamic
systems
in
coordination‐driven
metallo‐organic
cages
have
gained
significant
attentions
since
their
promising
applications
chiral
separation,
drug
delivery,
and
catalytical
fields.
To
maximize
guest‐binding
affinity,
hosts
adopting
multiple
conformations
are
widely
investigated
on
structural
flexibility
for
guest
accommodation.
In
this
study,
a
novel
cage
S
with
breathing
inner
cavity
freely
twisted
side
chains
was
proposed.
Single‐crystal
X‐ray
diffraction
analyses
depicted
characteristic
“breathing‐helical”
system
the
semiflexible
framework,
which
led
to
an
unprecedent
co‐crystallisation
of
racemic
symmetric
via
encapsulation
locking
C
70
guests.
By
taking
advantages
high
binding
selective
extraction
realized.
This
research
provides
new
ideas
modification
helicities
cages,
could
pave
way
advanced
conformational
manipulation
supramolecular
host
systems.
Chemistry of Materials,
Год журнала:
2024,
Номер
36(21), С. 10699 - 10709
Опубликована: Окт. 28, 2024
Metal–organic
cages
(MOCs)
as
artificial
mimic
enzymes
can
allow
small
organic
molecules
to
freely
move
in
and
out
of
the
cavity
with
confined
space,
which
often
increase
intermolecular
collisions
accelerate
those
reactions
that
are
difficult
occur.
This
kind
homogeneous
catalyst
possesses
high
catalytic
activity
regioselectivity,
attracting
growing
interest
recently.
However,
rational
design
MOCs
large
openings
well
rich
active
sites
for
efficient
chemical
conversions
remains
a
great
challenge.
Herein,
we
report
decanuclear
3d-4f
MOC,
Zn2Yb8,
hollow-walled
four
windows
self-assembled
cooperatively
by
bridging
ligands,
Zn-based
metalloligands,
lanthanide
Yb3+
ions.
The
lantern-like
Zn2Yb8
not
only
exposes
unblocked
passageways
allowing
more
guest
penetrate
cage
smoothly
but
also
provides
Lewis
centers
within
cavity,
could
promote
nucleophilic
additions
effectively
boost
Friedel–Crafts
alkylation
three-component
Strecker
reaction.
With
catalyst,
than
13
bis(indolyl)methane
derivatives
be
synthesized
easily
53–98%
through
alkylation,
conversion
reaction
aniline,
benzaldehyde,
trimethylsilyl
cyanide
achieve
approximately
98%
3
h.
Furthermore,
host–guest
relationship
investigations
confirmed
function
mainly
attributed
synergy
inherent
confinement
effect,
multiple
sites,
electrostatic
interactions
coordination
cage.
construction
discrete
MOC
its
applications
may
represent
potential
approach
developing
enzyme-like
supramolecular
nanoreactors.
Advanced Functional Materials,
Год журнала:
2024,
Номер
35(3)
Опубликована: Сен. 20, 2024
Abstract
Chiral
metallacages,
with
their
precisely
distributed
luminescent
and
chiral
units
inherent
adaptive
chirality,
represent
an
ideal
framework
for
developing
circularly
polarized
luminescence
(CPL)‐active
materials.
Despite
potential,
enhancing
the
dissymmetry
factor
(
g
lum
)
of
metallacage‐based
materials
remains
a
significant
challenge.
In
this
study,
useful
approach
is
proposed
by
co‐assembling
donor
metallacage
Δ
4
/
Λ
‐Zn
A
achiral
acceptor
Nile
red
(NiR),
achieving
efficient
energy
chirality
transfer
resulting
in
enhanced
CPL
these
co‐assemblies.
More
importantly,
microfluidic
laminar
flow
utilized,
known
providing
stable
driving
forces
confined
spaces,
to
achieve
marked
improvement
values
co‐assemblies
within
polymethyl
methacrylate
(PMMA)
films.
Computational
fluid
dynamics
(CFD)
simulations
small‐angle
X‐ray
scattering
(SAXS)
experiments
confirm
that
films
containing
/NiR,
prepared
via
chips,
display
well‐defined
distributions
metallacages
NiR
due
controllable
assembly
process
facilitated
flow.
This
work
pioneers
new
methodology
significantly
enhance
materials,
opening
avenues
field
photonics.
