Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(23)
Published: April 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.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(42)
Published: May 22, 2023
Abstract
Aromatic
units
tethered
with
an
azo
(−N=N−)
functionality
comprise
a
unique
class
of
compounds,
known
as
molecular
photoswitches,
exhibiting
reversible
transformation
between
their
E
‐
and
Z
‐isomers
in
response
to
photo‐irradiation.
Photoswitches
have
been
explored
extensively
the
recent
past
prepare
dynamic
self‐assembled
materials,
optoelectronic
devices,
responsive
biomaterials,
more.
Most
such
materials
involve
azobenzenes
photoswitch
date,
SciFinder
lists
more
than
7000
articles
1000
patents.
Subsequently,
great
deal
effort
has
invested
improve
photo‐isomerization
efficiency
related
mesoscopic
properties
azobenzenes.
Recently,
azoheteroarenes
cyclic
azobenzenes,
arylazopyrazoles,
arylazoisoxazoles,
arylazopyridines,
diazocines,
emerged
second
generation
photoswitches
beyond
conventional
These
offer
distinct
photoswitching
behavior
which
make
them
highly
promising
candidates
for
multifaceted
applications
ranging
from
photoresponsive
photopharmacophores.
In
this
minireview,
we
introduce
structural
refinement
diazocines
summarize
state‐of‐the‐art
on
utilizing
these
building
blocks
supramolecular
assembly,
material
science
photopharmacology,
highlighting
versatile
photochemical
behavior,
enhanced
functionality,
latest
applications.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(11), P. 3872 - 3878
Published: Jan. 1, 2024
Simple
structural
modifications
significantly
boost
the
photochromic
performance
of
imine-based
photoswitches.
This
work
lays
a
foundation
for
exploring
new
motifs
in
light-addressable
dynamic
combinatorial
chemistry.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(23)
Published: April 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.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
62(1)
Published: Oct. 10, 2022
We
report
on
two
regioisomeric,
diazocine
ligands
1
and
2
that
can
both
be
photoswitched
between
the
E-
Z-configurations
with
violet
green
light.
The
self-assembly
of
four
species
(1-Z,
1-E,
2-Z,
2-E)
CoII
ions
was
investigated
upon
changing
coordination
vectors
as
a
function
ligand
configuration
(E
vs
Z)
regioisomer
(1
2).
With
1-Z,
Co2
(1-Z)3
self-assembled,
while
mixture
ill-defined
(oligomers)
observed
2-Z.
Upon
photoswitching
385
nm
to
E
configurations,
opposite
1-E
forming
oligomers
2-E
(2-E)3
.
Light-controlled
dis/assembly
demonstrated
in
competition
experiment
sub-stoichiometric
amounts
ions;
alternating
irradiation
light
resulted
reversible
transformation
over
multiple
cycles
without
significant
fatigue
by
photoswitching.
Inorganic Chemistry,
Journal Year:
2024,
Volume and Issue:
63(15), P. 6692 - 6700
Published: April 4, 2024
The
fabrication
of
molecular
crystalline
materials
with
fast,
multistimuli-responsive
behavior
and
the
construction
corresponding
structure–activity
relationship
are
extraordinary
significance
for
development
smart
materials.
In
this
context,
three
functional
metal–organic
polyhedra
(MOP),
{[Dy2(bcbp)3(NO3)1.5(H2O)7]·Cl4.2·(NO3)0.3·H2O}n
(1),
{[Dy2(bcbp)4(H2O)8]Cl6}n
(2),
{[Eu2(bcbp)4(H2O)10]Cl6·H2O}n
(3;
bcbp
=
1,1′-bis(4-carboxyphenyl)-4,4′-bipyridinium),
were
successfully
prepared
characterized.
All
compounds
exhibit
rapid
reversible
photochromic
electrochromic
dual-responsive
behaviors.
Furthermore,
benefiting
from
well-defined
crystal
structure
different
responsive
behaviors,
photoinduced
electron
transfer
(PIET)
process
explored.
addition,
considering
excellent
performance,
function
filter
paper
organic
glass
used
ink-free
printing
UV
light
detection.
European Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
26(18)
Published: March 3, 2023
Abstract
The
introduction
of
enhanced
functionalization
is
a
key
aspect
in
the
current
design
cage
chemistry.
At
moment,
several
approaches
are
intensively
investigated.
synthesis
compounds
that
display
endohedral
plays
role
among
them.
Here,
studies
reactions
occur
endohedral‐functionalized
reviewed.
After
an
trends
cage‐chemistry
discussion
endohedral‐cage
divided
into
three
sections.
These
are:
1)
Endohedral
groups
by
themselves
functional,
2)
can
bind
to
transition‐metal
complex
and
3)
metal.
article
closes
with
outlook
on
additional
developments
field
cage‐compounds,
which
may
contribute
future
towards
reactivity
compounds.
ChemPlusChem,
Journal Year:
2023,
Volume and Issue:
88(12)
Published: Aug. 28, 2023
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.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(46), P. 31892 - 31900
Published: Nov. 5, 2024
The
ubiquitous
ability
of
natural
dynamic
nanostructures
to
adapt
environmental
changes
is
a
highly
desirable
property
for
chemical
systems,
particularly
in
the
development
complex
matter,
molecular
machines,
and
life-like
materials.
Designing
such
systems
challenging
due
generation
mixtures
with
responses
that
are
difficult
predict,
characterize,
diversify.
Here,
we
navigate
between
self-assembled
architectures
using
light
by
operating
an
intrinsic
photoswitchable
building
block
governs
state
system.
When
complementary
units
present,
photoswitch
determines
predominant
architecture,
reversibly
adapting
cage
macrocycles,
including
(otherwise
inaccessible)
higher-energy
assemblies.
Our
study
showcases
this
concept
seven
different
transformations,
offering
unprecedented
degree
control,
diversification,
adaptation
self-selecting
units.
These
findings
could
enable
applications
on-demand
dissipative
macrocycles
based
on
bonds.
We
also
envision
transient
nanostructures,
e.g.,
reticular
polymeric
materials,
being
explored
fine-tuning
nature
unit.
Chemistry - A European Journal,
Journal Year:
2023,
Volume and Issue:
29(21)
Published: Jan. 23, 2023
Natural
machinery
such
as
proteins
and
enzymes
can
bind
substrates
perform
intricate
functions
on
these
molecules.
This
behaviour
is
mediated
by
highly
ordered
but
conformationally
flexible
structures
dictated
through
favourable
intra-
intermolecular
interactions.
Metallosupramolecular
architectures
(MSAs)
function
synthetic
that
are
responsive
to
their
environment,
display
similar,
less
impressive,
abilities
biological
counterparts.
systems
share
the
properties
of
molecular
recognition
catalysis
facilitated
often
complex
architectures.
article
outlines
efforts
use
metallosupramolecular
mimic
machines
using
important
recent
examples
from
field.
