Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 27, 2025
Electron
donor–acceptor
complexes
are
commonly
employed
to
facilitate
photoinduced
radical-mediated
organic
reactions.
However,
achieving
these
photochemical
processes
with
catalytic
amounts
of
donors
or
acceptors
can
be
challenging,
especially
when
aiming
reduce
catalyst
loadings.
Herein,
we
have
unveiled
a
framework-based
heterogenization
approach
that
significantly
enhances
the
photoredox
activity
perylene
diimide
species
in
radical
addition
reactions
alkyl
silicates
by
promoting
faster
and
more
efficient
electron
complex
formation.
Besides
offering
broad
substrate
scope
alkene
hydroalkylation,
newly
developed
heterogeneous
photocatalysis
substantially
improves
turnover
numbers
comparison
previous
homogeneous
photocatalytic
systems
demonstrates
outstanding
recyclability.
These
research
findings
pave
way
for
advancement
various
practical
transformations
using
framework-supported
organocatalysts.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
147(9), P. 7849 - 7858
Published: Feb. 21, 2025
De
novo
protein
design
provides
a
framework
to
test
our
understanding
of
function
and
build
proteins
with
cofactors
functions
not
found
in
nature.
Here,
we
report
the
designed
bind
powerful
photooxidants
evaluation
use
these
generate
diffusible
small-molecule
reactive
species.
Because
excited-state
dynamics
are
influenced
by
hydration
photooxidant's
environment,
it
was
important
only
binding
site
but
also
evaluate
its
dynamic
properties.
Thus,
used
computational
conjunction
molecular
(MD)
simulations
protein,
designated
NBP
(NDI
Binding
Protein),
that
held
naphthalenediimide
(NDI),
photooxidant,
programmable
environment.
Solution
NMR
confirmed
structure
complex.
We
evaluated
two
NDI
this
de
using
ultrafast
pump-probe
spectroscopy
light-triggered
intra-
intermolecular
electron
transfer
function.
Moreover,
demonstrated
utility
platform
activate
multiple
probes
for
labeling.
ACS Applied Materials & Interfaces,
Journal Year:
2023,
Volume and Issue:
15(25), P. 30320 - 30331
Published: June 13, 2023
[Ru(Phen)3]2+
(phen
=
phenanthroline)
as
a
very
classical
photosensitizer
possesses
strong
absorption
in
the
visible
range
and
facilitates
photoinduced
electron
transfer,
which
plays
vital
role
regulating
photochemical
reactions.
However,
it
remains
significant
challenge
to
utilize
more
adequately
exploit
efficiently
ruthenium-based
materials
due
uniqueness,
scarcity,
nonrenewal
of
noble
metal.
Here,
we
integrate
intrinsic
advantages
mesoporous
metal-organic
frameworks
(meso-MOFs)
into
photosensitizer-embedded
heterometallic
Ni(II)/Ru(II)
meso-MOF
(LTG-NiRu)
via
metalloligand
approach.
LTG-NiRu,
with
an
extremely
robust
framework
large
one-dimensional
(1D)
channel,
not
only
makes
ruthenium
units
anchored
inner
wall
tubes
circumvent
problem
product/catalyst
separation
recycling
catalysts
heterogeneous
systems
but
also
exhibits
exceptional
activities
for
aerobic
photocatalytic
oxidative
coupling
amine
derivatives
general
photocatalyst.
The
conversion
light-induced
reaction
various
benzylamines
is
∼100%
1
h,
than
20
chemical
products
generated
by
cycloaddition
N-substituted
maleimides
N,N-dimethylaniline
can
be
synthesized
easily
presence
LTG-NiRu
upon
light
irradiation.
Moreover,
experiments
demonstrate
that
excellent
photocatalyst
high
stability
reusability.
represents
great
potential
photosensitizer-based
platform
efficient
oxidation
function
convenient
gram-scale
synthesis.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(13), P. 9293 - 9301
Published: March 22, 2024
Self-assembly-based
structural
transition
has
been
explored
for
various
applications,
including
molecular
machines,
sensors,
and
drug
delivery.
In
this
study,
we
developed
new
redox-active
metal–organic
frameworks
(MOFs)
called
DGIST-10
series
that
comprise
π-acidic
1,4,5,8-naphthalenediimide
(NDI)-based
ligands
Ni2+
ions,
aiming
to
boost
ligand-self-assembly-driven
study
the
involved
mechanism.
Notably,
during
synthesis
of
MOFs,
a
single-crystal–amorphous–single-crystal
occurred
within
MOFs
upon
radical
formation,
which
was
ascribed
fact
radicals
prefer
spin-pairing
or
through-space
electron
delocalization
by
π-orbital
overlap.
The
radical-formation-induced
transitions
were
further
confirmed
postsynthetic
solvothermal
treatment
isolated
nonradical
MOF
crystals.
transient
amorphous
phase
without
morphological
disintegration
clearly
observed,
contributing
seminal
change
MOF.
We
believe
unprecedented
triggered
ligand
self-assembly
magnifies
flexibility
diversity
is
one
pivotal
aspects
MOFs.
