Chemistry - A European Journal,
Journal Year:
2023,
Volume and Issue:
30(10)
Published: Dec. 9, 2023
The
construction
of
an
all-in-one
catalyst,
in
which
the
photosensitizer
and
transition
metal
site
are
close
to
each
other,
is
important
for
improving
efficiency
metallaphotoredox
catalysis.
However,
development
convenient
synthetic
strategies
precise
catalyst
remains
a
challenging
task
due
requirement
installation
catalytic
sites.
Herein,
we
have
successfully
established
facile
bottom-up
strategy
direct
synthesis
Ni(II)-incorporated
covalent
organic
framework
(COF),
named
LZU-713@Ni,
as
versatile
catalyst.
LZU-713@Ni
showed
excellent
activity
recyclability
photoredox/nickel-catalyzed
C-O,
C-S,
C-P
cross-coupling
reactions.
Notably,
this
displayed
better
than
its
homogeneous
analogues,
physically
mixed
dual
system,
and,
especially,
LZU-713/Ni
was
prepared
through
post-synthetic
modification.
improved
should
be
attributed
implementation
strategy,
incorporated
fixed,
ordered,
abundant
sites
into
framework.
This
work
sheds
new
light
on
exploration
concise
effective
multifunctional
COF-based
photocatalysts.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(11), P. 9055 - 9076
Published: May 29, 2024
Metallaphotoredox
catalysis
can
unlock
useful
pathways
for
transforming
organic
reactants
into
desirable
products,
largely
due
to
the
conversion
of
photon
energy
chemical
potential
drive
redox
and
bond
transformation
processes.
Despite
importance
these
processes
cross-coupling
reactions
other
transformations,
their
mechanistic
details
are
only
superficially
understood.
In
this
review,
we
have
provided
a
detailed
summary
various
photoredox
mechanisms
that
been
proposed
date
Ni-bipyridine
(bpy)
complexes,
focusing
separately
on
photosensitized
direct
excitation
reaction
By
highlighting
multiple
key
findings,
depict
how
mechanisms,
which
ultimately
define
substrate
scope,
themselves
defined
by
ground-
excited-state
geometric
electronic
structures
Ni-based
intermediates.
We
further
identify
knowledge
gaps
motivate
future
studies
development
synergistic
research
approaches
spanning
physical,
organic,
inorganic
chemistry
communities.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(22), P. 15331 - 15344
Published: May 23, 2024
Within
the
context
of
Ni
photoredox
catalysis,
halogen
atom
photoelimination
from
has
emerged
as
a
fruitful
strategy
for
enabling
hydrogen
transfer
(HAT)-mediated
C(sp3)–H
functionalization.
Despite
numerous
synthetic
transformations
invoking
this
paradigm,
unified
mechanistic
hypothesis
that
is
consistent
with
experimental
findings
on
catalytic
systems
and
accounts
radical
formation
facile
C(sp2)–C(sp3)
bond
remains
elusive.
We
employ
kinetic
analysis,
organometallic
synthesis,
computational
investigations
to
decipher
mechanism
prototypical
Ni-catalyzed
photochemical
arylation
reaction.
Our
revise
previous
proposals,
first
by
examining
relevance
SET
EnT
processes
intermediates
relevant
HAT-based
investigation
highlights
ability
blue
light
promote
efficient
Ni–C(sp2)
homolysis
cationic
NiIII
reductive
elimination
bipyridine
NiII
complexes.
However
interesting,
rates
selectivities
these
do
not
account
productive
pathway.
Instead,
our
studies
support
involves
evolution
in
situ
generated
dihalide
intermediates,
capture
NiII(aryl)(halide)
resting
state,
key
C–C
NiIII.
Oxidative
addition
NiI,
opposed
Ni0,
rapid
NiIII/NiI
comproportionation
play
roles
process.
The
presented
herein
offer
fundamental
insight
into
reactivity
broader
catalysis.
ACS Catalysis,
Journal Year:
2025,
Volume and Issue:
15(3), P. 1635 - 1654
Published: Jan. 15, 2025
Metallaphotoredox
cross
coupling
(MCC)
is
ranking
among
the
most
advanced
synthetic
methodology
as
it
can
access
chemical
space
that
difficult
to
attain
under
conventional
conditions.
Earlier
developed
MCC
mandates
an
independent
transition
metal
catalyst
and
respective
photocatalyst,
thus
constituting
a
dual
catalytic
manifold.
Complementarily,
paradigm-shifting
metallaphotoredox
strategy
capitalizes
on
single
photoreactive
complex
emerging,
which
brings
not
only
operational
simplification
but
also
unexpected
mechanistic
insights.
This
perspective
compiled
recent
advances
in
monocatalytic
couplings
categorized
them
based
ligands
confer
distinct
photoreactivities
various
mechanisms.
To
this
end,
ligand-enabled
oxidative
addition,
transmetalation,
reductive
elimination
other
radical-involving
pathways
were
summarized
with
notable
examples.
In
way,
we
wish
provide
handy
guideline
for
readers
who
are
interested
emerging
field
inspire
more
future
endeavors
MCCs
beyond.
ACS Catalysis,
Journal Year:
2025,
Volume and Issue:
unknown, P. 4665 - 4680
Published: March 5, 2025
Transition
metal
catalysis
is
an
indispensable
tool
for
organic
synthesis
that
has
been
harnessed,
modulated,
and
perfected
many
decades
by
careful
selection
of
centers
ligands,
giving
rise
to
synthetic
methods
with
unparalleled
efficiency
chemoselectivity.
Recent
developments
have
demonstrated
how
light
irradiation
can
also
be
recruited
as
a
powerful
dramatically
alter
the
outcome
catalytic
reactions,
providing
access
innovative
pathways
remarkable
potential.
In
this
context,
adoption
photochemical
conditions
mainstream
strategy
drive
reactions
unveiled
exciting
opportunities
exploit
rich
excited-state
framework
transition
metals
applications.
This
Perspective
examines
advances
in
application
complexes
standalone
photocatalysts,
exploiting
innate
reactivity
their
excited
states
beyond
common
use
photoredox
catalysts.
An
account
relevant
examples
dissected
provide
discussion
on
electronic
reorganization,
orbitals
involved,
associated
different
types
states.
analysis
aims
practitioners
fundamental
principles
guiding
strategies
understand,
design,
apply
light-activation
homogeneous
synthesis.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(46)
Published: Sept. 26, 2022
We
demonstrate
that
several
visible-light-mediated
carbon-heteroatom
cross-coupling
reactions
can
be
carried
out
using
a
photoactive
NiII
precatalyst
forms
in
situ
from
nickel
salt
and
bipyridine
ligand
decorated
with
two
carbazole
groups
(Ni(Czbpy)Cl2
).
The
activation
of
this
towards
follows
hitherto
undisclosed
mechanism
is
different
previously
reported
light-responsive
complexes
undergo
metal-to-ligand
charge
transfer.
Theoretical
spectroscopic
investigations
revealed
irradiation
Ni(Czbpy)Cl2
visible
light
causes
an
initial
intraligand
transfer
event
triggers
productive
catalysis.
Ligand
polymerization
affords
porous,
recyclable
organic
polymer
for
heterogeneous
catalysis
reactions.
catalyst
shows
stable
performance
packed-bed
flow
reactor
during
week
continuous
operation.
Nature Communications,
Journal Year:
2023,
Volume and Issue:
14(1)
Published: March 17, 2023
Abstract
The
development
of
heterogeneous
metallaphotocatalysis
is
great
interest
for
sustainable
organic
synthesis.
rational
design
and
controllable
preparation
well-defined
(site-isolated)
metal/photo
bifunctional
solid
catalysts
to
meet
such
goal
remains
a
critical
challenge.
Herein,
we
demonstrate
the
incorporation
privileged
homogeneous
bipyridyl-based
Ni-catalysts
into
highly
ordered
crystalline
potassium
poly(heptazine
imide)
(K-PHI).
A
variety
PHI-supported
cationic
(L
n
Ni-PHI)
have
been
prepared
fully
characterized
by
various
techniques
including
NMR,
ICP-OES,
XPS,
HAADF-STEM
XAS.
L
Ni-PHI
exhibit
exceptional
chemical
stability
recyclability
in
diverse
C−P,
C−S,
C−O
C−N
cross-coupling
reactions.
proximity
cooperativity
effects
significantly
enhances
photo/Ni
dual
catalytic
activity,
thus
resulting
low
catalyst
loadings
high
turnover
numbers.
Chemistry - A European Journal,
Journal Year:
2023,
Volume and Issue:
29(37)
Published: April 17, 2023
This
paper
reports
a
photochemical
C-N
coupling
of
abundant,
but
less
reactive
aryl
chlorides,
with
structurally
diverse
primary
and
secondary
amides
by
Ni-mediated
without
an
external
photocatalyst.
Under
the
irradiation
light
(390-395
nm)
soluble
organic
amine
as
base,
reaction
allows
for
successful
transformation
(hetero)aryl
chlorides
to
wide
range
N-aryl
amides.
More
than
60
examples
are
shown,
demonstrating
feasibility
applicability
this
protocol
in
synthesis.
Mechanic
studies
indicate
that
amidation
proceeds
via
Ni(I)-Ni(III)
catalytic
cycle.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(37), P. 25832 - 25840
Published: Sept. 4, 2024
The
connectivity
(valency)
of
building
blocks
for
constructing
3D
covalent
organic
frameworks
(COFs)
has
long
been
limited
to
4,
6,
8,
and
12.
Developing
a
higher
remains
great
challenge
in
the
field
COF
structural
design.
Herein,
this
work
reports
hierarchical
expansion
strategy
making
16-connected
construct
COFs
with
sqc
topology.
[16
+
2]
construction
achieved
by
condensation
between
carbazolyl
dicyanobenzene-based
block
(CzTPN)
linear
diamino
linkers
(BD
or
Bpy)
affords
two
(named
CzBD
CzBpy
COF).
Furthermore,
attributed
well-organized
donor-acceptor
(D-A)
heterojunction,
Ni
chelated
(Ni@CzBpy
COF)
exhibits
excellent
performance
photoredox/Ni
dual
catalytic
C(sp