Angewandte Chemie,
Год журнала:
2024,
Номер
137(1)
Опубликована: Окт. 24, 2024
Abstract
Heterometallic
cluster‐based
materials
offer
the
potential
to
incorporate
multiple
functionalities,
leveraging
aggregation
effects
of
clusters
and
translating
this
heterogeneity
complexity
into
unexpected
properties
that
are
more
than
just
sum
their
components.
However,
rational
construction
heterometallic
remains
challenging
due
metal
cation
coordination
structural
unpredictability.
This
minireview
provides
insights
a
general
synthetic
strategy
based
on
Hard
Soft
Acids
Bases
(HSAB)
theory,
summarizing
its
advantages
in
designed
synthesis
discrete
(intracluster
assembly)
infinite
(intercluster
assembly).
Furthermore,
it
emphasizes
exploit
intrinsic
mixed
components
achieve
breakthroughs
across
broad
range
applications.
The
from
review
expected
drive
progress
controllable
predictable
manner.
Nature Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 8, 2025
Abstract
The
creation
of
hosts
capable
accommodating
different
guest
molecules
may
enable
these
to
play
useful
roles
in
chemical
purifications,
among
other
applications.
Metal–organic
cages
are
excellent
for
various
guests,
but
they
generally
incorporate
rigid
structural
units
that
hinder
dynamic
adaptation
specific
guests.
Here
we
report
a
conformationally
adaptable
pseudo-cubic
cage
can
dynamically
increase
its
cavity
volume
fit
guests
with
differing
sizes.
This
pseudo-cube
incorporates
tetramine
subcomponent
2,6-naphthalene
arms
cooperatively
adopt
non-planar
conformation,
enabling
the
faces
switch
between
endo
and
exo
states.
A
wide
range
were
observed
bind
within
this
cage,
spanning
sizes
from
46%
154%
empty
cage.
Experimental
computational
evidence
characterizes
flipping
,
expanding
upon
binding
larger
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(31), С. 21677 - 21688
Опубликована: Июль 23, 2024
Achieving
high
guest
loading
and
multiguest-binding
capacity
holds
crucial
significance
for
advancement
in
separation,
catalysis,
drug
delivery
with
synthetic
receptors;
however,
it
remains
a
challenging
bottleneck
characterization
of
high-stoichiometry
guest-binding
events.
Herein,
we
describe
large-sized
coordination
cage
(MOC-70-Zn
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
64(1)
Опубликована: Окт. 24, 2024
Heterometallic
cluster-based
materials
offer
the
potential
to
incorporate
multiple
functionalities,
leveraging
aggregation
effects
of
clusters
and
translating
this
heterogeneity
complexity
into
unexpected
properties
that
are
more
than
just
sum
their
components.
However,
rational
construction
heterometallic
remains
challenging
due
metal
cation
coordination
structural
unpredictability.
This
minireview
provides
insights
a
general
synthetic
strategy
based
on
Hard
Soft
Acids
Bases
(HSAB)
theory,
summarizing
its
advantages
in
designed
synthesis
discrete
(intracluster
assembly)
infinite
(intercluster
assembly).
Furthermore,
it
emphasizes
exploit
intrinsic
mixed
components
achieve
breakthroughs
across
broad
range
applications.
The
from
review
expected
drive
progress
controllable
predictable
manner.
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)
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(47), С. 32748 - 32756
Опубликована: Ноя. 17, 2024
A
family
of
Pd2L4
cages
prepared
from
ligands
based
on
an
axially
chiral
diamino-[1,1′-biazulene]
motif
(serving
as
a
unique
azulene-based
surrogate
the
ubiquitous
BINOL
moiety)
is
reported.
We
show
that
preparing
cage
starting
racemate
shorter
bis-monodentate
ligand
derivative,
equipped
with
pyridine
donor
groups,
leads
to
integrative
("social")
self-sorting,
exclusively
yielding
meso-trans
product,
but
only
in
selection
solvents.
This
phenomenon
driven
by
individual
solvent
molecules
acting
hydrogen
bonding
tethers
between
amino
groups
neighboring
ligands,
thereby
locking
final
coordination
single
isomeric
form.
The
experimental
(solvent-dependent
NMR,
single-crystal
X-ray
diffraction)
observations
this
cooperative
interaction
could
be
explained
computational
analyses
when
explicit
solvation
was
considered.
Furthermore,
we
larger
isoquinoline
donors,
which,
unlike
first
one,
does
not
undergo
social
self-sorting
its
racemic
mixture,
further
highlighting
importance
solvents
bridging
short
distances
groups.
Homochiral
formed
ligand,
however,
furnish
cavity
can
bind
anionic
and
neutral
metal
complexes
such
[Pt(CN)6]2–
Cr(CO)6
discriminate
two
enantiomers
guest
camphor
sulfonate.
Inorganic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 23, 2025
Two
enantiomers
of
the
cage-type
complex,
[Co3LR2]
and
[Co3LS2]
a
large
hexaazatriphenolic
[3
+
3]
macrocyclic
imine
L,
have
been
synthesized
characterized
on
basis
NMR,
CD,
ESI
MS
spectra.
The
X-ray
crystal
structures
[Co3L2]
crystalline
forms
reveal
two
macrocycles
cone
shape
stitched
together
by
three
Co(II)
ions,
forming
barrel-shaped
molecule
with
central
void.
Because
limited
size
cavity
enantiopure
nature
these
enantiomeric
complexes,
both
size-selective
enantioselective
binding
guest
molecules
are
observed.
In
case
chiral
guests,
interaction
paramagnetic
centers
leads
to
an
effective
NMR
enantiodifferentiation
signals
molecules,
even
at
host:guest
ratios
as
low
1:200.
tight
prochiral
such
ethanol
isopropanol
within
results
in
splitting
enantiotopic
methylene
methyl
signals.
dc
magnetic
data
for
accord
presence
high-spin
ac
susceptibility
this
complex
indicate
field-induced
single
magnet
(SMM)
behavior.
contrast
reaction
Co(II),
ligand
H3L
Ni(II)
or
Cu(II)
salts
contraction
macrocycle
formation
complexes
smaller
[2
2]
macrocycle.
Nature Communications,
Год журнала:
2025,
Номер
16(1)
Опубликована: Апрель 28, 2025
Photoinduced
dearomatization
of
arenes
is
a
powerful
strategy
in
organic
synthesis
to
disrupt
the
stable
aromaticity;
however,
asymmetric
photocatalysis
unactivated
remains
highly
challenging
and
rare.
Herein
we
demonstrate
an
enzyme-mimicking
cage-confined
visible-light
method
for
intramolecular
dearomative
cycloaddition
with
electron-deficient
β-aryl
enones.
Owing
multi-functional
synergy
chirality,
energy
transfer,
host-guest
interactions
confined
microenvironments,
self-assembled
chiral
cage-photoreactor
could
pre-organize
activate
enones
give
stereoselectively
fused
cyclobutanes
through
induced
[2
+
2]
ortho-cycloaddition.
Notably,
competing
transformation
[4
cycloadducts
has
been
inhibited,
producing
thermodynamically
unfavorable
excellent
regio-,
diastereo-,
enantioselectivities.
Advanced Functional Materials,
Год журнала:
2025,
Номер
unknown
Опубликована: Май 28, 2025
Abstract
Metal–organic
frameworks
(MOFs)
represent
an
emerging
class
of
crystalline
materials
characterized
by
high
porosity,
vast
surface
area,
and
structural
variability.
Despite
the
potential
for
sustainable
energy
applications,
challenges
remain
in
designing
engineering
MOF
powders
with
limited
mechanical
robustness
integrity
into
self‐standing,
durable
membranes
while
retaining
their
functionality.
Inspired
unique
structure
natural
vascular
bundles,
approach
is
developed
to
fabricating
via
dimensional
reduction
superstructures.
Interestingly,
water‐flexibility
superstructure
led
homogeneous
gelation,
which
can
encapsulate
a
substantial
amount
water
molecules
within
porous
structures,
forming
micro/nano‐scale
channels
efficient
proton
transport.
Hierarchical
channel
ensures
super‐protonic
conductivity
values
ranging
from
0.07
S
cm
−1
(40%
RH)
at
293
K
0.14
(90%
353
K.
For
first
time,
it
demonstrates
relevant
hydrogen
fuel
cell
performance,
achieving
peak
power
density
48
mW
−2
.
This
study
paves
way
all‐MOF‐based
as
proton‐conducting
low‐temperature
cells.
Herein,
we
report
the
self-assembly
of
a
D3-symmetric
quasi-icosahedron
4
based
on
desymmetrized
terpyridine
ligand.
The
participant
triflimide
(NTf2-)
interacts
with
rectangular
aperture,
templating
generation
4.
With
addition
other
smaller
anions
(50-90
Å3)
into
4,
supramolecular
conversion
to
highly
symmetric
(O)
cuboctahedron
5
can
be
observed
due
optimizing
binding
capabilities
between
and
apertures
metallo-organic
cages.
This
enables
selective
tight
multiple
anion
bindings
clear
mechanism
has
been
utilized
facilitate
dissociation
lithium-anion
pairs
immobilization
in
lithium
metal
batteries.
Introducing
solid
polymer
electrolytes
increase
ion
transference
number
t+
0.78,
significantly
enhancing
conductivity
within
electrolyte
enriching
flux
for
transport.
Consequently,
composite
exhibits
excellent
transport
kinetics,
thereby
endowing
batteries
superior
electrochemical
performance.
