Research Square (Research Square),
Год журнала:
2023,
Номер
unknown
Опубликована: Дек. 6, 2023
Abstract
Despite
having
significant
applications
in
the
construction
of
controlled
delivery
systems
with
high
anti-interference
capability,
dual-controlled
molecular
release
has
not
yet
been
achieved
based
on
small
molecular/supramolecular
entities.
Herein,
we
report
a
system
coordination
cages,
for
which
releasing
guest
from
cage
demands
synchronously
altering
coordinative
metal
cations
and
solvent.
The
Hg5L2
Ag5L2,
are
constructed
via
coordination-driven
self-assembly
corannulene-based
ligand.
While
shows
solvent-independent
encapsulation
all
studied
solvents,
Ag5L2
is
able
to
encapsulate
guests
only
some
such
as
acetone-d6,
but
will
liberate
encapsulated
1,1,2,2-tetrachloroethane-d2.
interconvertible.
Thus,
acetone-d6
can
be
achieved,
requires
two
separate
operations,
including
substitutions
change
In
chemistry,
this
have
potential
programmable
synthesis,
cooperating
single-controlled
sequentially
different
reactants/catalysts.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(15), С. 10234 - 10239
Опубликована: Апрель 5, 2024
Simple
organic
ligands
can
self-assemble
with
metal
ions
to
generate
metal–organic
cages,
whose
cavities
bind
guests
selectively.
This
binding
may
enable
new
methods
of
chemical
separation
or
sensing,
among
other
useful
functions.
Here
we
report
the
preparation
a
CuI6L4
pseudo-octahedral
cage,
which
from
simple
building
blocks.
Temperature,
solvent,
and
presence
different
governed
structure
predominated
dynamic
mixture
cage
diastereomers
arrangements
right-
left-handed
vertices.
Dissolution
in
dimethyl
sulfoxide
tetrahedral
led
chiral
T-symmetric
framework,
whereas
low
temperatures
favored
achiral
S4-symmetric
diastereomer.
Tetrahedral
long
arms
were
encapsulated
form
mechanically
bonded
suit[4]anes,
guest
protruding
out
through
host
windows.
The
was
also
observed
fluorinated
steroids,
an
important
class
drug
molecules,
but
not
non-fluorinated
providing
basis
for
processes.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(11), С. 7811 - 7821
Опубликована: Март 7, 2024
Spin-crossover
(SCO)
coordination
cages
are
at
the
forefront
of
research
for
their
potential
in
crafting
next-generation
molecular
devices.
However,
due
to
scarcity
SCO
hosts
and
own
limited
cavities,
interplay
between
host
multiple
guests
binding
has
remained
elusive.
In
this
contribution,
we
present
a
family
pseudo-octahedral
(M6L4,
M
=
ZnII,
CoII,
FeII,
NiII)
assembled
from
tritopic
tridentate
ligand
L
with
metal
ions.
The
utilization
FeII
ion
leads
successful
creation
Fe6L4-type
cage.
Host–guest
studies
these
M6L4
reveal
capacity
encapsulate
four
adamantine-based
guests.
Notably,
spin
transition
temperature
T1/2
Fe6L4
is
dependent
on
encapsulated.
inclusion
adamantine
yields
an
unprecedented
shift
54
K,
record
guest-mediated
date.
This
drastic
ascribed
synergistic
effect
coupled
optimal
fit
within
host.
Through
straightforward
thermodynamic
cycle,
affinities
high-spin
(HS)
low-spin
(LS)
states
separated
apparent
constant.
result
indicates
that
LS
state
stronger
affinity
than
HS
state.
Exploring
thermodynamics
host–guest
complexes
allows
us
examine
cavity.
study
reveals
can
be
manipulated
by
encapsulation
guests,
cage
ideal
candidate
determining
guest
fit.
Chemical Society Reviews,
Год журнала:
2024,
Номер
53(21), С. 10380 - 10408
Опубликована: Янв. 1, 2024
Stemming
from
early
seminal
notions
of
molecular
recognition
and
encapsulation,
three-dimensional,
cavity-containing
capsular
compounds
assemblies
have
attracted
intense
interest
due
to
the
ability
modulate
chemical
physical
properties
species
encapsulated
within
these
confined
spaces
compared
bulk
environments.
With
such
a
diverse
range
covalent
motifs
non-covalent
(supramolecular)
interactions
available
assemble
building
blocks,
an
incredibly
wide-range
capsular-type
architectures
been
developed.
Furthermore,
synthetic
tunability
internal
environments
gives
chemists
opportunity
engineer
systems
for
uses
in
sensing,
sequestration,
catalysis
transport
molecules,
just
name
few.
In
this
tutorial
review,
overview
is
provided
into
design
principles,
synthesis,
characterisation,
structural
facets
coordination
cages,
porous
organic
supramolecular
capsules,
foldamers
mechanically
interlocked
molecules.
Using
recent
examples,
advantages
limitations
each
system
are
explored,
highlighting
their
application
various
tasks
functions.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(23)
Опубликована: Апрель 3, 2024
Abstract
Controlling
supramolecular
systems
between
different
functional
forms
by
utilizing
acids/bases
as
stimuli
is
a
formidable
challenge,
especially
where
labile
coordination
bonds
are
involved.
A
pair
of
acid/base
responsive,
interconvertible
1,5‐enedione/pyrylium
based
Pd
2
L
4
‐type
cages
prepared
that
exhibit
differential
guest
binding
abilities
towards
disulfonates
varied
sizes.
three‐state
switch
has
been
achieved,
(i)
weakly
coordinating
base
induced
cage‐to‐cage
transformation
in
the
first
step,
(ii)
strongly
triggered
cage
disassembly
second
and
(iii)
third
step
shows
acid(strong)
promoted
generation
initial
cage,
thereby
completing
cycle.
To
our
surprise,
specific
disulfonate
facilitated
transformations
inducing
strain
on
assembly
opening
pyrylium
rings
cage.
Through
competitive
study,
we
demonstrated
superior
capability
octacationic
pyrylium‐based
over
similar‐sized
tetracationic
These
results
provide
reliable
approach
to
reversibly
modulate
properties
acid/base‐responsive
self‐assembled
cages.
Crystal Growth & Design,
Год журнала:
2024,
Номер
24(8), С. 3449 - 3457
Опубликована: Апрель 2, 2024
Supramolecular
isomerism
has
been
recognized
as
an
effective
strategy
for
manipulating
structures
and
properties,
particularly
in
metal–hydrogen-bonded
organic
frameworks
(MHOFs).
However,
it
less
studied
the
context
of
magnetic
dynamics.
In
this
study,
we
reinvestigated
two
previously
reported
cobalt(II)
HOFs,
{[(H2O)2Co(Hbic)2]·sol}n
(H2bic
=
1H-benzimidazole-5-carboxylic
acid;
1,
Sol
2DMF·1.5H2O;
2,
H2O),
which
exhibit
unique
supramolecular
isomerism.
both
complexes,
octahedral
Co(II)
ions
are
connected
by
deprotonated
Hbic-ligands
to
form
one-dimensional
chains,
then
sustained
into
three-dimensional
prominent
N–H···O
hydrogen-bonding
interactions.
This
results
significantly
different
porosities
N2-adsorption
abilities:
a
high
solvent-accessible
void
46.2%
desolvated
phase
compared
only
2.3%
that
likely
due
additional
π–π
stacking
Interestingly,
our
studies
revealed
1
2
typical
single
ion
magnet
behaviors,
with
alternating
relaxation
dynamics
(Raman,
direct,
QTM
1;
Raman
direct
2).
These
findings
demonstrate
structures,
stability,
porosities,
properties
MHOF
materials
can
be
effectively
tuned
through
isomerization
approach.
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.
Inorganic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 11, 2025
Supramolecular
metal–organic
cages
(MOCs)
have
gained
attention
as
versatile
catalytic
platforms
due
to
their
self-assembled
architectures
and
well-defined
cavities,
which
mimic
enzyme
active
sites
enable
spatial
confinement.
This
confinement
modulates
the
reaction
pathways
enhances
performance.
Recent
studies
highlight
potential
in
various
organic
transformations,
but
factors
governing
MOC-catalyzed
reactions
remain
incompletely
understood.
work
builds
on
prior
computational
of
Diels–Alder
catalyzed
by
palladium-based
MOCs,
showing
that
common
view
transition-state
stabilization
via
π–π
interactions
is
not
valid.
Instead,
we
find
between
substrate
ligands
destabilize
transition
state.
Additionally,
theoretical
regioselectivity,
validated
experimentally,
suggest
encapsulation
efficiency
key
determining
selectivity.
These
findings
provide
new
insights
into
mechanisms
reactions.
Inorganic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 27, 2025
Metal–organic
cages
are
a
class
of
discrete
supramolecular
architectures
endowed
with
well-defined
cavity
and
diverse
functionalities,
offering
broad
range
applications
that,
however,
predominantly
confined
to
liquid
phases.
In
this
study,
we
present
the
self-assembly
Eu(III)4L4
tetrahedra,
constructed
from
triarylborane-cored
tritopic
tridentate
ligands,
which
were
fabricated
into
spin-coated
films
bright
emission,
smooth
surfaces,
uniform
thickness.
These
demonstrated
ultralow
detection
limits
for
series
volatile
amines,
reaching
sub-ppt
level.
This
work
serves
as
compelling
example
preparation
application
metal–organic-cage-based
films,
paving
way
broader
scenarios.