Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(36), P. 19925 - 19931
Published: Aug. 29, 2023
We
report
the
development
and
characterization
of
a
library
Ir(III)
photocatalysts
capable
undergoing
spin-forbidden
excitation
(SFE)
under
orange
light
irradiation
(595
nm).
These
catalysts
were
successfully
applied
to
construction
synthetically
valuable
C(sp2)-C(sp3)
bonds
inaccessible
with
existing
methods
low-energy
light-driven
dual
nickel/photoredox
catalysis,
demonstrating
synthetic
utility
this
photocatalyst
family.
The
are
accessing
both
oxidatively
reductively
activated
coupling
partners,
illustrated
through
deaminative
arylation
potassium
alkyl
trifluoroborate
cross-coupling
reactions
aryl
halides.
demonstrate
diverse
substrate
scopes
paradigms
mild
conditions
in
first
example
metallaphotoredox
coupling.
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.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(22), P. 12293 - 12304
Published: May 19, 2023
Recent
mechanistic
studies
of
dual
photoredox/Ni-catalyzed,
light-driven
cross-coupling
reactions
have
found
that
the
photocatalyst
(PC)
operates
through
either
reductive
quenching
or
energy
transfer
cycles.
To
date,
reports
invoking
oxidative
cycles
are
comparatively
rare
and
direct
observation
such
a
event
has
not
been
reported.
However,
when
PCs
with
highly
reducing
excited
states
used
(e.g.,
Ir(ppy)
Molecular
luminescent
materials
with
optical
waveguide
have
wide
application
prospects
in
light-emitting
diodes,
sensors,
and
logic
gates.
However,
the
majority
of
traditional
systems
are
based
on
brittle
molecular
crystals,
which
limited
fabrication,
transportation,
storage,
adaptation
flexible
devices
under
diverse
situations.
To
date,
design
synthesis
photofunctional
high
flexibility,
novel
waveguide,
multi-port
color-tunable
emission
same
solid-state
system
remain
an
open
challenge.
Here,
we
constructed
new
types
zero-dimensional
organic
metal
halides
(Au-4-dimethylaminopyridine
[DMAP]
In-DMAP)
a
rarely
elasticity
rather
low
loss
coefficients
for
waveguide.
Theoretical
calculations
intermolecular
interactions
showed
that
2
crystalline
was
original
from
their
herringbone
structure
slip
plane.
Based
one-dimensional
microrods
crystals
2-dimensional
microplate
Mn-DMAP,
heterojunctions
multi-color
space-resolved
waveguides
been
fabricated.
The
formation
mechanism
is
surface
selective
growth
account
lattice
mismatch
ratio
between
contacting
crystal
planes.
Therefore,
this
work
describes
first
attempt
to
metal-halide-based
flexibility
expanding
smart
devices,
such
as
gates
multiplexers.
Chemical Society Reviews,
Journal Year:
2023,
Volume and Issue:
52(16), P. 5373 - 5387
Published: Jan. 1, 2023
The
chemistry
and
the
reaction
mechanisms
behind
four
catalytic
protocols
currently
available
for
visible
light-induced
C–C
cross-coupling
by
activation
of
C
sp
3
–H
bonds
are
described.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(17), P. 9876 - 9885
Published: April 18, 2023
Herein,
we
report
a
redox-neutral
and
atom-economical
protocol
to
synthesize
valuable
alkenyl
chlorides
from
unactivated
internal
alkynes
abundant
organochlorides
via
photoredox
nickel
catalysis.
This
enables
the
site-
stereoselective
addition
of
chlorine
photoelimination-initiated
sequential
hydrochlorination/remote
C-H
functionalization.
The
is
compatible
with
wide
range
medicinally
relevant
heteroaryl,
aryl,
acid,
alkyl
for
efficiently
producing
γ-functionalized
chlorides,
exhibiting
excellent
regioselectivities
stereoselectivities.
Late-stage
modifications
synthetic
manipulations
products
preliminary
mechanistic
studies
are
also
presented.
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.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(46)
Published: Sept. 21, 2023
Square-planar
NiII
complexes
are
interesting
as
cheaper
and
more
sustainable
alternatives
to
PtII
luminophores
widely
used
in
lighting
photocatalysis.
We
investigated
the
excited-state
behavior
of
two
complexes,
which
isostructural
with
luminescent
complexes.
The
initially
excited
singlet
metal-to-ligand
charge
transfer
(1
MLCT)
states
decay
metal-centered
(3
MC)
within
less
than
1
picosecond,
followed
by
non-radiative
relaxation
3
MC
electronic
ground
state
9-21
ps.
This
contrasts
population
an
emissive
triplet
ligand-centered
LC)
upon
excitation
analogues.
Structural
distortions
responsible
for
this
discrepant
lead
dark
far
lower
energy
LC
compounds.
Our
findings
suggest
that
if
these
structural
could
be
restricted
rigid
coordination
environments
stronger
ligand
fields,
four-coordinate
decelerated
such
or
MLCT
become
accessible.
These
insights
relevant
make
fit
photophysical
photochemical
applications
relied
on
until
now.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(40), P. 27583 - 27593
Published: Sept. 26, 2024
The
exploration
of
strong
chemical
bonds
as
synthetic
handles
offers
new
disconnection
strategies
for
the
synthesis
functionalized
molecules
via
transition
metal
catalysis.
However,
slow
oxidative
addition
rate
these
covalent
to
a
center
hampers
their
utility.
Here,
we
report
C(sp
