Precise Assembly/Disassembly of Homo-Type and Hetero-Type Macrocycles with Photoresponsive and Non-Photoresponsive Dynamic Covalent Bonds
Organic & Biomolecular Chemistry,
Год журнала:
2025,
Номер
23(10), С. 2498 - 2509
Опубликована: Янв. 1, 2025
Dynamic
covalent
macrocycles
offer
the
advantage
of
tunable
ring-opening/ring-closure
and
structural
transformation,
but
their
control
with
precision
remains
a
daunting
task
due
to
labile
nature
reversible
bonds.
Herein
we
demonstrate
precise
formation/scission
varied
sizes
by
contrasting
reactivity,
stability,
degradability
light-active
light-inactive
dynamic
The
incorporation
photoswitchable
non-photoresponsive
aldehyde
sites
into
one
single
dialdehyde
component
afforded
creation
[1
+
1]
type
primary
diamines
suitable
lengths.
manipulation
light
acid/base
stimuli
allowed
on-demand
breaking/remaking
macrocycles,
achieving
interconversion
between
macrocyclic
linear
skeletons.
Moreover,
combination
dialdehyde,
diamines,
secondary
enabled
construction
hetero-type
[2
1
1']
via
enhanced
discrimination
hierarchical
assembly.
Light-induced
kinetic
locking/unlocking
bonds
further
macrocycle-to-macrocycle
conversion
when
needed.
Through
leveraging
controllable
connection/disconnection,
switchable
formation/disintegration
mechanically
interlocked
catenanes
was
accomplished.
results
described
showcase
potential
photoinduced
chemistry
for
preparing
complex
architectures
should
set
stage
molecular
recognition,
assemblies,
synthetic
motors,
responsive
materials.
Язык: Английский
Stimuli-Controlled Keto–Enol Tautomerism of Extended Unsaturated Carbonyls for Gating Photoswitching of Diarylethenes
Organic Letters,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 21, 2025
Gated
photoswitching
systems,
which
enable
control
over
photochromic
properties,
play
an
important
role
in
chemistry.
Here,
we
present
a
novel
gated
system
based
on
extended
unsaturated
1,3-dicarbonyl
derivatives
of
diarylethenes
by
manipulating
keto–enol
tautomerism.
While
the
intramolecular
charge
transfer
process
blocked
photochromism,
creation
ester
enabled
efficient
bidirectional
photoswitching.
The
use
acid/base
further
induced
shift
equilibrium.
Finally,
switchable
multistep
gating
photochrome
was
achieved,
enhancing
complexity.
Язык: Английский
All‐Visible‐Light Azobenzene Photoswitches for Controlling Dynamic C—N Bonds†
Chinese Journal of Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 16, 2025
Comprehensive
Summary
The
visible
light‐driven
photoswitches
are
attracting
widespread
attention,
but
it
is
challenging
to
leverage
their
phototriggered
structural
changes
regulate
dynamic
bonds,
assemblies,
and
materials.
Herein,
we
incorporated
reversible
covalent
sites
of
aldehyde
ring‐chain
tautomers
into
all‐visible‐light
azobenzenes
toward
a
versatile
platform
for
light‐controlled
formation/exchange
C—N
bonds
from
secondary
amines.
movement
equilibrium
was
attained
via
manipulating
intramolecular
multiple
hydrogen
bonding
E
/
Z
configurational
isomers.
Such
regulation
further
enabled
photocontrolled
kinetics
the
formation
exchange
reactions
cyclic
hemiaminal
ethers
amines
exhibiting
kinetic
rate
reversal
varied
capability
isomers
in
engaging
azo
attached
carboxylate
with
ammonium
salt
accounts
difference.
Moreover,
photoswitching
performance
different
solutions
readily
regulated
by
reactivity
control
light
associated
mechanistic
foundation
add
collection
photoswitchable
chemistry
would
lay
subsequent
biological
material
applications.
Язык: Английский
Photoswitchable Cascades for Allosteric and Bidirectional Control over Covalent Bonds and Assemblies
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
unknown
Опубликована: Апрель 15, 2024
Studies
of
complex
systems
and
emerging
properties
to
mimic
biosystems
are
at
the
forefront
chemical
research.
Dynamic
multistep
cascades,
especially
those
exhibiting
allosteric
regulation,
challenging.
Herein,
we
demonstrate
a
versatile
platform
photoswitchable
covalent
cascades
toward
remote
bidirectional
control
reversible
bonds
ensuing
assemblies.
The
relay
photochromic
switch,
keto–enol
equilibrium,
ring–chain
equilibrium
allows
light-mediated
structural
changes.
accompanying
distinct
reactivity
further
enables
dynamic
bonding
release
substrates
bidirectionally
through
alternating
two
wavelengths
light,
essentially
realizing
signaling
cycles.
downfall
energy
by
bond
formation/scission
upon
photochemical
reactions
offers
driving
force
for
controlled
direction
cascade.
To
show
molecular
diversity,
on-demand
assembly/disassembly
polymers,
including
structurally
reconfigurable
was
realized.
This
work
achieves
regulation
architectures
within
which
has
rarely
been
reported
before.
results
resemble
biological
networks
should
set
stage
many
endeavors,
such
as
assemblies,
motors,
responsive
intelligent
materials.
Язык: Английский
Second Generation Zwitterionic Aza‐Diarylethene: Photoreversible CN Bond Formation, Three‐State Photoswitching, Thermal Energy Release, and Facile Photoinitiation of Polymerization
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 21, 2024
Abstract
Diarylethenes
are
a
well‐studied
and
optimized
class
of
photoswitches
with
wide
range
applications,
including
data
storage,
smart
materials,
or
photocontrolled
catalysis
biological
processes.
Most
recently,
aza‐diarylethenes
have
been
developed
in
which
carbon‐carbon
bond
connections
replaced
by
carbon‐nitrogen
connections.
This
structural
elaboration
opens
up
an
entire
new
structure
property
space
expanding
the
versatility
applicability
diarylethenes.
In
this
work,
we
present
second
generation
zwitterionic
aza‐diarylethenes,
finally
allows
for
fully
reversible
photoswitching
precise
control
over
all
three
switching
states.
High‐yielding
between
neutral
open
form
Z
isomer
is
achieved
two
different
wavelengths
light.
The
third
E
isomeric
state
can
be
reached
to
87
%
upon
irradiation
wavelength.
Its
high
energy
content
>10
kcal/mol
released
thermally
deliberate
solvent
change
as
trigger
mechanism,
rendering
into
interesting
candidates
molecular
solar
thermal
storage
(MOST)
applications.
also
serves
locking
state,
allowing
toggle
light‐responsiveness
reversibly
labile
stable
switching.
Further,
states
leads
highly
efficient
photopolymerization
methyl
acrylate
(MA),
directly
harnessing
unleashed
chemical
reactivity
our
aza‐diarylethene
materials
application.
Язык: Английский
Second Generation Zwitterionic Aza‐Diarylethene: Photoreversible CN Bond Formation, Three‐State Photoswitching, Thermal Energy Release, and Facile Photoinitiation of Polymerization
Angewandte Chemie,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 21, 2024
Abstract
Diarylethenes
are
a
well‐studied
and
optimized
class
of
photoswitches
with
wide
range
applications,
including
data
storage,
smart
materials,
or
photocontrolled
catalysis
biological
processes.
Most
recently,
aza‐diarylethenes
have
been
developed
in
which
carbon‐carbon
bond
connections
replaced
by
carbon‐nitrogen
connections.
This
structural
elaboration
opens
up
an
entire
new
structure
property
space
expanding
the
versatility
applicability
diarylethenes.
In
this
work,
we
present
second
generation
zwitterionic
aza‐diarylethenes,
finally
allows
for
fully
reversible
photoswitching
precise
control
over
all
three
switching
states.
High‐yielding
between
neutral
open
form
Z
isomer
is
achieved
two
different
wavelengths
light.
The
third
E
isomeric
state
can
be
reached
to
87
%
upon
irradiation
wavelength.
Its
high
energy
content
>10
kcal/mol
released
thermally
deliberate
solvent
change
as
trigger
mechanism,
rendering
into
interesting
candidates
molecular
solar
thermal
storage
(MOST)
applications.
also
serves
locking
state,
allowing
toggle
light‐responsiveness
reversibly
labile
stable
switching.
Further,
states
leads
highly
efficient
photopolymerization
methyl
acrylate
(MA),
directly
harnessing
unleashed
chemical
reactivity
our
aza‐diarylethene
materials
application.
Язык: Английский
Rubizhne Institute – a Birthplace of Photochromic Molecules
The Chemical Record,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 3, 2024
Abstract
We
introduce
the
community
to
remarkable
fact
that
two
significant
discoveries
in
field
of
organic
photoswitches
are
associated
Rubizhne
(Rubezhnoe)
branch
Research
Institute
Organic
Intermediates
and
Dyes
during
last
century.
The
institute
was
a
place
where
researchers
various
nationalities
carried
out
studies
dyes
for
printing
textiles.
These
efforts
resulted
photoswitchable
hemithioindigos
by
M.
A.
Mostoslavskii
peri
‐aryloxyquinones
Yu.
E.
Gerasimenko.
Herein,
based
on
available
literature,
we
reconstruct
circumstances
surrounding
these
outstanding
findings
highlight
unique
role
as
research
center.
Furthermore,
demonstrate
impact
results
molecules.
Язык: Английский