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
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
Manipulating the Isomerization of a Tris-azobenzene Cage by Anion Binding
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 22, 2025
Here,
we
report
a
C3-symmetric
tris-azobenzene
cage
1
comprising
azobenzene
cores
and
bis(urea)
units.
This
system
demonstrates
efficient
reversible
photoisomerization
unprecedented
anion-mediated
switching
modes.
Specifically,
the
phosphate
anion
induces
concerted
ZZZ
→
EEE
isomerization
with
prolonged
thermal
relaxation
(t1/2
=
37.5
h
at
298
K).
In
contrast,
bulky
benzene-1,3,5-tricarboxylate
enforces
stepwise
pathway
(ZZZ
EZZ
EEZ
EEE)
rapid
54.4,
44.5,
12.9
min
for
each
step).
study
represents
first
demonstration
of
selective
control
over
multi-azobenzene
switch,
mimicking
biological
adaptability
through
environmental
changes.
Язык: Английский
Chiral Self‐Sorting Directed Supramolecular Organic Framework of Imine Cages for Iodine Capture
Small,
Год журнала:
2025,
Номер
unknown
Опубликована: Май 2, 2025
Abstract
Supramolecular
organic
frameworks
(SOFs)
with
nanotubular
pores,
assembled
through
weak
non‐covalent
interactions,
are
highly
sought‐after
for
storage,
separation,
and
pollutant
capture
but
limited.
Herein,
a
SOF
chiral
imine
cage
is
reported
by
leveraging
kinetically
driven
dynamic
covalent
chemistry,
self‐sorting,
dispersion
interactions
efficient
iodine
capture.
The
crystallization‐driven
synthesis
involves
triamine
racemic
mixture
of
axially
dialdehyde
equipped
in
bimesityl
(BM)
skeleton
that
undergoes
narcissistic
self‐sorting
to
form
homochiral
(BM‐PIC)
enantiomers,
which
result
the
(BM‐PIC‐SOF).
Notably,
excess
drives
into
heterochiral
cages
favorable
solvent.
BM‐PIC‐SOF
templated
solvent
molecules
features
pores
(1.4
nm)
stabilized
notably,
forces
between
mesitylene
rings.
Further,
kinetic
crystals
BM‐PIC‐SOF,
upon
exchange
volatile
solvents,
undergo
single‐crystal‐to‐single‐crystal
transformation
at
high
temperature
thermodynamic
polymorph
large
structural
difference.
demonstrates
remarkable
efficacy
adsorbing
not
only
from
vapor
(6.0
g.g
−1
)
also
(3.88
aqueous
mediums
(5.01
g
).
Язык: Английский
Harnessing light to drive a non-photoresponsive reaction out of equilibrium
Chem,
Год журнала:
2025,
Номер
unknown, С. 102579 - 102579
Опубликована: Май 1, 2025
Язык: Английский
Enhancing the Photoswitching Properties of N-Alkyl Imines
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Май 15, 2025
N-Alkyl
imines
are
prevalent
in
dynamic-covalent
chemistry
and
self-assembled
structures,
yet
their
E/Z
photochromism
is
often
overlooked
due
to
the
high-energy
light
required
for
isomerization.
Here,
we
present
a
simple
strategy
enhance
photoswitching
properties,
achieving
switching
wavelengths
photostationary
state
distributions
comparable
azobenzene.
Moreover,
demonstrate
that
these
N-alkyl
undergo
photoisomerization
condensed
phase
exhibit
isomer-dependent
fluorescence.
We
anticipate
this
study
will
inspire
design
of
photoresponsive
architectures
operate
directly
at
bond,
eliminating
need
dedicated
photoswitchable
motifs.
Язык: Английский