Angewandte Chemie,
Год журнала:
2024,
Номер
136(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.
Chemical Society Reviews,
Год журнала:
2023,
Номер
52(13), С. 4392 - 4442
Опубликована: Янв. 1, 2023
Metal
agents
have
made
incredible
strides
in
preclinical
research
and
clinical
applications,
but
their
short
emission/absorption
wavelengths
continue
to
be
a
barrier
distribution,
therapeutic
action,
visual
tracking,
efficacy
evaluation.
Abstract
Responsive
materials
can
respond
to
different
external
stimuli
by
changing
their
chemical
or/and
physical
properties,
thus
being
useful
for
various
applications
such
as
drug
delivery,
bioimaging,
actuators,
and
sensors.
A
common
strategy
constructing
responsive
is
introduce
dynamic
covalent
bonds
or
noncovalent
interactions
into
polymer
systems.
Compared
with
other
bonds,
coordination
have
the
peculiarity
that
bond
strength
dissociation
rate
be
tuned
a
greater
extent.
Such
tunability
makes
uniquely
advantageous
in
stimuli‐responsive
materials.
Herein,
we
summarize
recent
progress
of
based
on
are
classified
seven
categories,
is,
thermo‐responsive,
photo‐responsive,
electro‐responsive,
mechano‐responsive,
chemo‐responsive,
pH‐responsive,
materials,
according
type
stimuli.
The
corresponding
mechanism,
design
strategy,
research
status
each
category
comprehensively
summarized.
Finally,
prospects
challenges
development
discussed.
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.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(32), С. 17845 - 17855
Опубликована: Авг. 7, 2023
Charge
plays
a
crucial
role
in
the
function
of
molecular
and
supramolecular
systems,
but
coordination
hosts
capable
orthogonal
charge
regulation
remain
elusive
so
far.
In
this
study,
we
report
condition-dependent
self-assembly
charge-reversible
lanthanide–organic
tetra-capped
octahedral
cages,
i.e.,
[Ln6(H3L)4]6+
[Ln6L4]6–,
from
series
lanthanide
ions
(Ln3+;
Ln
=
Lu,
Yb,
Eu)
tritopic
tetradentate
acylhydrazone
ligand
(H6L)
featuring
multiple
deprotonation
states
propeller
conformations.
While
direct
under
basic
conditions
produced
mixture
various
ΔxΛ6–x-[Ln6L4]6–
(x
0–6)
stereoisomers,
racemic
Δ6-
Λ6-[Ln6L4]6–
could
be
exclusively
obtained
first
Λ6-[Ln6(H3L)4]6+
neutral
followed
by
post-assembly
deprotonation.
Rich
isomerism
on
cages
arising
coupling
between
metal-centered
Δ/Λ
chirality
conformations
has
been
discussed
based
X-ray
single-crystal
structures
C3-symmetric
Δ3Λ3-Ln6L4
T-symmetric
Δ6/Λ6-Ln6L4
complexes.
Host–guest
studies
confirmed
that
positively
charged
rac-Δ6/Λ6-[Ln6(H3L)4]6+
bind
anionic
sulfonates,
negatively
rac-Δ6/Λ6-[Ln6L4]6–
exhibited
strong
encapsulation
ability
toward
ammonium
guests,
where
acid/base-triggered
guest
uptake/release
realized
taking
advantage
reversibility
cage.
Moreover,
photophysical
revealed
visible-light-sensitized
guest-encapsulation-enhanced
NIR
emissions
rac-Δ6/Λ6-Yb6L4
This
work
not
only
enriches
library
functional
also
provides
promising
candidate
with
for
development
smart
materials.
Accounts of Materials Research,
Год журнала:
2024,
Номер
5(9), С. 1109 - 1120
Опубликована: Авг. 1, 2024
ConspectusIntelligent
supramolecular
assemblies
can
respond
well
to
external
stimuli
such
as
pH,
temperature,
light,
electricity,
magnetism,
and
enzymes
achieve
not
only
reversible
topological
morphology
changes
assembly/disassembly
processes
but
also
special
physical
chemical
properties,
which
are
successfully
applied
biological
imaging,
cancer
treatment,
luminescent
materials,
anticounterfeiting,
sensing,
molecular
switch
in
chemical,
research
fields.
Among
all
stimuli-responsive
assemblies,
light-controlled
have
always
attracted
intense
attention
because
light
is
a
kind
of
clean
eco-friendly
energy.
In
this
Account,
we
focus
on
formed
by
four
types
photoresponsive
molecules
macrocyclic
hosts
cucurbit[n]urils,
cyclodextrins,
crown
ethers,
their
regulations
materials
bioimaging.
The
cascade
between
photoisomerization
or
photoreaction
mainly
include:
1)
based
macrocycles
diarylethene.
As
switches,
the
open-ring
closed-ring
configurations
diarylethenes
be
reversibly
controlled
tunable
fluorescence
resonance
energy
transfer
(FRET)
process
further
regulate
behaviors
construct
intelligent
response
cell-imaging,
multicolor
luminescence
systems.
2)
Light-controlled
spiropyran.
Different
from
diarylethenes,
spiropyran
converse
positive
charges
ring-open
merocyanie
(MC)
state,
amphiphilic
easy
bond
with
like
neutral/negative
ring-closed
(SP)
more
likely
self-assemble.
Therefore,
differentiation
bonding
affinities
MC
SP
light-driven
machines.
3)
azobenzene,
whether
azobenzene
modified
functional
guests,
through
host–guest
interactions,
behavior
regulated
apply
catalytic
activity
modulation,
induction
microtubule
(MT)
assembly/disassembly,
drug
delivery,
others.
4)
anthracene,
different
anthracene
before
after
photooxidation
hosts,
dimerization,
change
morphologies
drive
phosphorescence
dual
imaging
construction
photostimuli-driven
lanthanide
switch.
With
creation
novel
building
units
modifications
molecules,
consider
that
innovation
growth
should
widely
used
material
conversion,
real-time
cell
targeted
organic
optoelectronic
machines,
photocatalysis
reactions.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(33), С. 18607 - 18622
Опубликована: Авг. 11, 2023
Coordination-driven
self-assembly
enables
the
spontaneous
construction
of
metallo-supramolecules
with
high
precision,
facilitated
by
dynamic
and
reversible
metal-ligand
interactions.
The
nature
coordination,
however,
results
in
structural
lability
many
metallo-supramolecular
assembly
systems.
Consequently,
it
remains
a
formidable
challenge
to
achieve
reversibility
stability
simultaneously
To
tackle
this
issue,
herein,
we
incorporate
an
acid-/base-responsive
tridentate
ligand
into
multitopic
building
blocks
precisely
construct
series
cages
through
coordination-driven
self-assembly.
These
cagelike
assemblies
can
be
transformed
their
static
states
mild
situ
deprotonation/oxidation,
leading
ultrastable
skeletons
that
withstand
temperatures,
metal
ion
chelators,
strong
acid/base
conditions.
This
transformation
provides
reliable
powerful
approach
manipulate
kinetic
features
allows
for
modulation
encapsulation
release
behaviors
metallo-cages
when
utilizing
nanoscale
quantum
dots
(QDs)
as
guest
molecules.
The
construction
of
large
and
complex
supramolecular
architectures
through
self-assembly
is
at
the
forefront
contemporary
coordination
chemistry.
Notwithstanding
great
success
in
various
systems
using
anionic
bridges
(e.g.,
O