Solid-State Photoswitching of Hydrazones Based on Excited-State Intramolecular Proton Transfer
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 8, 2025
The
development
of
new
photochromic
systems
is
motivated
by
the
possibility
controlling
properties
and
functions
materials
with
high
spatial
temporal
resolution
in
a
reversible
manner.
While
there
are
several
classes
photoswitches
operating
solution,
design
efficiently
solid
state
remains
highly
challenging,
mainly
due
to
limitations
related
confinement
effects.
Triaryl-hydrazones
represent
relatively
subclass
bistable
hydrazone
exhibiting
efficient
Z/E
photochromism
solution.
As
"large
volume"
photoswitches,
they
have
been
anticipated
display
only
limited
solid-state
photoswitching.
Here,
we
show
that
Z
isomers
newly
prepared
triaryl-hydrazones
containing
perfluorinated
hydrazine
phenyl
ring
(PHZs)
exhibit
impressive
an
unexpected
light-induced
red-shift
absorption
maximum.
Based
on
(time-dependent)
density
functional
theory
calculations,
photoswitching
reaction
mechanism
involving
excited
intramolecular
proton
transfer
has
proposed,
which
rationalizes
observed
formation
metastable
structure.
Advanced
experimental
techniques
including
X-ray
diffraction,
NMR
EPR
spectroscopy,
confocal
Raman
microscopy
corroborated
suggested
revealed
superficial
phenomenon.
This
atypical
behavior
PHZs
can
also
be
realized
using
visible
light
form
thin
films,
manifests
their
potential
use
optics
optoelectronics.
Language: Английский
Switching from Molecules to Functional Materials: Breakthroughs in Photochromism With MOFs
Advanced Materials,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Oct. 7, 2024
Abstract
Photochromic
materials
with
properties
that
can
be
dynamically
tailored
as
a
function
of
external
stimuli
are
rapidly
expanding
field
driven
by
applications
in
areas
ranging
from
molecular
computing,
nanotechnology,
or
photopharmacology
to
programable
heterogeneous
catalysis.
Challenges
arise,
however,
when
translating
the
rapid,
solution‐like
response
stimuli‐responsive
moieties
solid‐state
due
intermolecular
interactions
imposed
through
close
packing
bulk
solids.
As
result,
integration
photochromic
compounds
into
synthetically
porous
matrices,
such
metal‐organic
frameworks
(MOFs),
has
come
forefront
an
emerging
strategy
for
material
development.
This
review
highlights
how
core
principles
reticular
chemistry
(on
example
MOFs)
play
critical
role
performance,
surpassing
limitations
previously
observed
solution
solid
state.
The
symbiotic
relationship
between
photoresponsive
and
focus
on
synthesis
creates
avenues
toward
tailorable
photoisomerization
kinetics,
directional
energy
charge
transfer,
switchable
gas
sorption,
synergistic
chromophore
communication
is
discussed.
not
only
focuses
recent
cutting‐edge
advancements
development,
but
also
novel,
vital‐to‐pursue
pathways
multifaceted
functional
realms
energy,
technology,
biomedicine.
Language: Английский
Delignification of wood and infiltration with alumina/polyvinylpyrrolidone nanofiber-reinforced nanocomposite toward photoluminescent smart window for detection and filtration of ultraviolet radiation
Journal of Photochemistry and Photobiology A Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown, P. 116456 - 116456
Published: April 1, 2025
Language: Английский