Angewandte Chemie,
Год журнала:
2024,
Номер
136(20)
Опубликована: Фев. 21, 2024
Abstract
Post‐synthetic
modification
plays
a
crucial
role
in
precisely
adjusting
the
structure
and
functions
of
advanced
materials.
Herein,
we
report
self‐assembly
tubular
heterometallic
Pd
3
Cu
6
L1
capsule
that
incorporates
Pd(II)
CuL1
metalloligands.
This
undergoes
further
with
two
tridentate
anionic
ligands
(L2)
to
afford
bicapped
L2
2
an
Edshammer
polyhedral
structure.
By
employing
transition
metal
ions,
acid,
oxidation
agents,
can
be
converted
into
uncapped
one.
form
then
revert
back
on
addition
Br
−
ions
base.
Interestingly,
introducing
Ag
+
leads
removal
one
ligand
from
capsule,
yielding
mono‐capped
Furthermore,
size
anions
critically
influences
precise
control
over
post‐synthetic
modifications
capsules.
It
was
demonstrated
these
capsules
selectively
encapsulate
tetrahedral
anions,
offering
novel
approach
for
design
intelligent
molecular
delivery
systems.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(4), С. 2568 - 2573
Опубликована: Янв. 17, 2024
Chemical
separations
are
expensive,
consuming
10–15%
of
humanity's
global
energy
budget.
Many
current
separation
methods
employ
thermal
for
distillation,
often
through
the
combustion
carbon-containing
fuels,
or
extractions
and
crystallizations
from
organic
solvents,
which
must
then
be
discarded
redistilled,
with
a
substantial
energetic
cost.
The
direct
use
renewable
sources,
such
as
light,
could
enable
development
novel
processes,
is
required
transition
away
fossil
fuel
use.
Metal–organic
capsules,
can
selectively
bind
molecules
mixtures,
provide
foundation
these
processes.
Here
we
report
tetrahedral
metal–organic
capsule
bearing
light-responsive
diazo
moieties
around
its
metal-ion
vertices.
This
used
to
separate
progesterone
mixture
steroids
in
process
driven
by
visible
light
energy.
Our
combines
biphasic
extraction
selective
binding
light-driven
release
this
molecule
purified
form.
Ultimately,
our
might
adapted
purifications
many
other
fine
chemical
products
that
bound
capsules.
Chemical Society Reviews,
Год журнала:
2024,
Номер
53(12), С. 6042 - 6067
Опубликована: Янв. 1, 2024
This
review
comprehensively
summarizes
the
development
of
supramolecular
cages
as
carriers
and
channels
for
cargo
transport
in
abiotic
biological
systems.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(19), С. 13210 - 13225
Опубликована: Май 6, 2024
A
new
class
of
photoswitchable
NHC
ligands,
named
azImBA,
has
been
developed
by
integrating
azobenzene
into
a
previously
unreported
imidazobenzoxazol-1-ylidene
framework.
These
rigid
photochromic
carbenes
enable
precise
control
over
confinement
around
metal's
coordination
sphere.
As
model
system,
gold(I)
complexes
these
NHCs
exhibit
efficient
bidirectional
E–Z
isomerization
under
visible
light,
offering
versatile
platform
for
reversibly
photomodulating
the
reactivity
organogold
species.
Comprehensive
kinetic
studies
protodeauration
reaction
reveal
rate
differences
up
to
2
orders
magnitude
between
E
and
Z
isomers
NHCs,
resulting
in
quasi-complete
visible-light-gated
ON/OFF
switchable
system.
Such
high
level
photomodulation
efficiency
is
unprecedented
gold
complexes,
challenging
current
state-of-the-art
organometallics.
Thorough
investigations
ligand
properties
paired
with
structure–reactivity
correlations
underscored
unique
ligand's
steric
features
as
key
factor
reactivity.
This
effective
photocontrol
strategy
was
further
validated
catalysis,
enabling
situ
photoswitching
catalytic
activity
intramolecular
hydroalkoxylation
-amination
alkynes.
Given
significance
findings
its
potential
widely
applicable,
easily
customizable
ancillary
platform,
azImBA
poised
stimulate
development
adaptive,
multifunctional
metal
complexes.
The
utilisation
of
light
to
achieve
precise
manipulation
and
control
over
the
structure
function
supramolecular
assemblies
has
emerged
as
a
highly
promising
approach
in
development
complex,
configurable,
or
multifunctional
systems
nanoscopic
machine-like
entities.
In
this
minireview,
we
highlight
recent
examples
self-assembled
covalently
bound
cages
macrocycles
with
focus
on
external
internal
functionalisation
photoswitchable
unit
embedment
photoswitch
into
framework
structure.
Functionalising
interior
exterior
cage
macrocycle
photoresponsive
group
enables
different
properties,
such
guest
binding
assembly
solid-state,
while
overall
shape
often
undergoes
no
significant
change.
By
directly
integrating
structure,
isomerisation
can
either
induce
geometry
change,
disassembly,
disassembly
reassembly
Historical
covered
review
are
based
azobenzene,
diarylethene,
stilbene
photoswitches,
alkene
motors
that
were
incorporated
constructed
by
metal-organic,
dynamic
covalent,
covalent
bonds.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(51)
Опубликована: Ноя. 6, 2023
Abstract
The
phosphate‐coordination
triple
helicates
A
2
L
3
(A=anion)
with
azobenzene‐spaced
bis‐bis(urea)
ligands
(L)
have
proven
to
undergo
a
rare
in
situ
photoisomerization
(without
disassembly
of
the
structure)
rather
than
typically
known,
stepwise
“disassembly‐isomerization‐reassembly”
process.
This
is
enabled
by
structural
self‐adaptability
“aniono”
assembly
arising
from
multiple
relatively
weak
and
flexible
hydrogen
bonds
between
phosphate
anion
bis(urea)
units.
Notably,
Z→E
thermal
relaxation
rate
isomerized
azobenzene
unit
significantly
decreased
(up
20‐fold)
for
compared
free
ligands.
Moreover,
binding
chiral
guest
cations
inside
cavity
Z
‐isomerized
helicate
can
induce
optically
pure
diastereomers,
thus
demonstrating
new
strategy
making
light‐activated
chiroptical
materials.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(36)
Опубликована: Июнь 13, 2024
New
stimulus-responsive
scaffolds
are
of
interest
as
constituents
hierarchical
supramolecular
ensembles.
1,3,5-2,4,6-Functionalized,
facially
segregated
benzene
moieties
have
a
time-honored
role
building
blocks
for
host
molecules.
However,
their
user
switchable
motifs
in
the
construction
multi-component
structures
remains
poorly
explored.
Here,
we
report
molecular
cage
1,
which
consists
bent
anthracene
dimer
3
paired
with
1,3,5-tris(aminomethyl)-2,4,6-triethylbenzene
2.
As
result
pH-induced
ababab↔bababa
isomerization
constituent-functionalized
units
derived
from
2,
this
can
reversibly
convert
between
an
open
state
and
closed
form,
both
solution
solid
state.
Cage
1
was
used
to
create
stimuli-responsive
superstructures,
namely
Russian
doll-like
complexes
[K⊂18-crown-6⊂1]
Chemical Science,
Год журнала:
2024,
Номер
15(22), С. 8488 - 8499
Опубликована: Янв. 1, 2024
Inclusion
of
photoswitchable
azobenzene
units
as
spacers
into
ditopic
bridging
ligands
Lm
and
Lp,
containing
two
chelating
pyrazolyl-pyridine
termini,
allows
formation
metal
complex
assemblies
with
Co(ii)
that
undergo
a
range
light-induced
structural
transformations.
One
notable
result
is
the
conversion
Co2(Lp)3
dinuclear
triple
helicate
(based
on
E
ligand
isomer)
to
C
3-symmetric
Co4(Lp)6
assembly,
assumed
be
an
edge-bridged
tetrahedral
cage,
based
Z
isomer.
Another
preparation
series
Co4(Lm)6
complexes,
which
Co4(E-Lm)6
was
crystallographically
characterised
consists
pair
Co2(Lm)2
double
helicates
connected
by
additional
span
units,
giving
cyclic
Co4
array
in
one
then
alternate
around
periphery.
A
set
complexes
could
prepared
different
ratios
:
isomers
(0
6,
2
4,
4
6
0)
Co4(Z-Lm)2(E-Lm)4
particularly
stable
dominated
speciation
behaviour,
either
during
switching
geometry
pre-formed
or
when
were
combined
proportions
preparation.
These
examples
(i)
interconversion
between
Co2L3
(helicate)
(ii)
Co4L6
(cage)
Co4(Z-Lm)n(E-Lm)6-n
Lm,
constitute
significant
advances
field
supramolecular
assemblies.
