Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(34)
Published: June 12, 2024
Abstract
Proton‐coupled
electron
transfer
(PCET)
imparts
an
energetic
advantage
over
single
in
activating
inert
substances.
Natural
PCET
enzyme
catalysis
generally
requires
tripartite
preorganization
of
proton
relay,
substrate‐bound
active
center,
and
redox
mediator,
making
the
processes
efficient
precluding
side
reactions.
Inspired
by
this,
a
heterogeneous
photocatalytic
system
was
established
to
achieve
higher
driving
forces
modifying
relays
into
anthraquinone‐based
anionic
coordination
polymers.
The
proximally
separated
photoredox‐mediating
anthraquinone
moiety
allowed
pre‐assembly
substrate
between
them,
merging
unsaturated
bonds
photoreductive
PCET,
which
enhanced
reaction
kinetics
compared
with
counter
catalyst
without
relay.
This
method
applied
broad‐scoped
reduction
aryl
ketones,
carbonyls,
aromatic
compounds.
distinctive
regioselectivities
for
isoquinoline
derivatives
were
found
occur
on
carbon‐ring
sides.
PCET‐generated
radical
intermediate
quinoline
could
be
trapped
alkene
relay‐assisted
Minisci
addition,
forming
pharmaceutical
aza
‐acenaphthene
scaffold
within
one
step.
When
using
heteroatom(X)−H/C−H
compounds
as
proton‐electron
donors,
this
protocol
activate
these
through
photooxidative
afford
radicals
trap
them
electron‐deficient
compounds,
furnishing
direct
X−H/C−H
functionalization.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(36)
Published: July 19, 2023
Metal-organic
frameworks
(MOFs)
with
expanding
porosity
and
tailored
pore
environments
are
intriguing
for
catalytic
applications.
We
report
herein
a
straightforward
method
of
controlled
partial
linker
thermolysis
to
introduce
desirable
mesopores
into
mono-ligand
MOFs,
which
is
different
from
the
classical
thermolyzing
that
starts
mixed-linker
MOFs.
UiO-66-NH2
,
after
ligand
thermolysis,
exhibits
significant
mesoporosity,
retained
crystal
structure,
improved
charge
photogeneration
abundant
anchoring
sites,
ideal
explore
single-site
photocatalysis.
Atomically
dispersed
Cu
then
accommodated
in
pore.
The
resulting
catalyst
excellent
performance
photocatalytic
alkylation
oxidation
coupling
functionalization
terminal
alkynes.
study
highlights
advantage
synthesize
hierarchical
MOFs
achieve
advanced
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(16), P. 9198 - 9206
Published: April 17, 2023
Aryl-ketone
derivatives
have
been
acknowledged
as
promising
organic
photocatalysts
for
photosynthesis.
However,
they
are
limited
by
their
photostability
and
less
explored
photoinduced
electron
transfer
(PET)
applications.
Herein
we
demonstrate
a
novel
strategy
to
cover
the
shortage
of
aryl-ketone
control
photoreactivity
implanting
symmetric
aryl
ketones
into
conjugated
covalent
frameworks
(COFs).
To
prove
concept,
three
comparative
materials
with
same
topology
varied
electronic
structures
were
built,
adopting
truxenone
knot
functionalized
terephthalaldehyde
linkers.
Spectroscopic
investigation
excited
carrier
dynamics
analysis
disclosed
improvements
in
efficiency
well
structure-performance
relationships
toward
N-aryl
tetrahydroisoquinoline
oxidation.
This
system
provides
robust
rule
thumb
designing
new-generation
photocatalysts.
Energy & Environmental Science,
Journal Year:
2024,
Volume and Issue:
17(6), P. 2260 - 2268
Published: Jan. 1, 2024
Metal–salophen
organic
frameworks
with
dispersed
metal
centers
and
precise
coordination
environments
were
synthesized.
The
optimal
sample
exhibited
great
photocatalytic
activity
near-unity
CO
selectivity
over
a
wide
range
of
2
concentrations.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(11)
Published: Jan. 13, 2024
Abstract
Modifying
redox
potential
of
substrates
and
intermediates
to
balance
pairs
steps
are
important
stages
for
multistep
photosynthesis
but
faced
marked
challenges.
Through
co‐clathration
iridium
photosensitizer
imine
substrate
within
one
packet
a
metal‐organic
capsule
shift
the
potentials
substrate,
herein,
we
reported
multiphoton
enzymatic
strategy
generation
heterocycles
by
intramolecular
C−X
hydrogen
evolution
cross‐couplings.
The
cage
facilitated
pre‐equilibrium
substrate‐involving
clathrate
that
cathodic
shifts
oxidation
substrate‐dye‐host
ternary
complex
configuration
inversion
via
spatial
constraints
in
confined
space.
new
two
photon
excitation
enabled
precise
control
electron
transfer
between
each
pair
(photosensitizer,
capsule),
endowing
catalytic
system
proceeding
smoothly
with
an
fashion.
Three
kinds
2‐subsituted
(−OH,
−NH
2
,
−SH)
imines
N‐aryl
enamines
all
give
corresponding
cyclization
products
efficiently
under
visible
light
irradiation,
demonstrating
promising
microenvironment
driven
thermodynamic
activation
host‐dye‐substrate
synergistic
combination
photocatalytic
transformations.
ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
13(15), P. 9969 - 9978
Published: July 17, 2023
The
complex
and
precise
structure
of
natural
monooxygenases
makes
it
difficult
to
clone
their
activity,
the
reported
artificial
copper-based
monooxygenase
catalysts
for
oxidation
inert
C(sp3)–H
bonds
exhibit
limited
catalytic
activities.
Inspired
by
monooxygenases,
we
report
a
metal–organic
framework
(SiW12@CuMOF-1)
comprising
binuclear
copper
HAT
catalyst,
photosensitizing
nicotinamide
adenine
dinucleotide
(NAD+)
mimic
bridging
ligand,
embedded
polyoxometalate.
SiW12@CuMOF-1
accelerates
oxidative
dehydrogenation
3,5-DTBC
with
efficiency
comparable
that
polyphenol
oxidase.
In
presence
pyridine
hydrochloride,
irradiation
afforded
highly
active
chlorine
radical
CuI
species
via
ligand-to-metal
charge
transfer
process.
abstracts
hydrogen
atom
selectively
from
generate
intermediate.
interacted
oxygen
1O2
formed
photoinduced
energy
excited
state
NAD+
mimics,
giving
O2•–
further
oxidization.
well-modified
sites
cleave
O–O
bond
give
final
products
selectively.
Meanwhile,
polyoxometalates
alcohol
substrates
bonding
interactions
help
conversion
high
efficiency.
well-defined
structural
characters,
finely
modified
properties,
sustainable
multiphoton
excitation
photocatalytic
processes
provide
new
avenue
develop
robust
enzymes
uniform
improved
performances.
Chemistry - A European Journal,
Journal Year:
2024,
Volume and Issue:
30(24)
Published: Feb. 19, 2024
Abstract
It
is
challenging
to
realize
the
selective
C−C
bond
cleavage
of
lignin
β‐O‐4
linkages
for
production
high‐value
aromatic
chemicals
due
its
intrinsic
inertness
and
complex
structure.
Here
we
report
a
light‐driven,
chlorine‐radical‐based
protocol
oxidative
in
various
model
compounds
catalyzed
by
commercially
available
TPT
CaCl
2
,
achieving
high
conversion
good
product
yields
at
room
temperature.
Mechanistic
studies
reveal
that
preferential
activation
C
β
−H
facilitates
oxidation
via
chlorine
radical.
Furthermore,
this
method
also
applicable
depolymerization
natural
extracts,
furnishing
oxygenates
from
α
−C
bonds.
This
study
provides
experimental
foundations
valorization
into
value‐added
compounds.
Chemical Society Reviews,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Dec. 20, 2024
Mixed-valence
MOFs
have
exhibited
unique
features
in
different
practical
fields,
resulting
from
long-range
charge
delocalization
and
a
tunable
band
gap
within
the
framework.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(27), P. 10308 - 10349
Published: Jan. 1, 2024
Recent
progresses
in
Cu–oxygen
adducts
towards
recalcitrant
C–H
activation
are
reviewed
with
focus
on
Cu
metalloenzymes
and
bioinspired
synthetic
models,
mono-
to
polynuclear
complexes,
working
under
homogeneous
heterogeneous
catalytic
conditions.
