Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(48)
Published: Aug. 16, 2023
In
the
past
80
years,
fluoropolymers
have
found
broad
applications
in
both
industrial
and
academic
settings,
owing
to
their
unique
physicochemical
properties.
Copolymerizations
of
fluoroalkene
feedstocks
present
an
important
avenue
obtain
high-performance
materials
by
merging
intrinsic
attributes
fluorocarbons
great
versatility
comonomers.
Recently,
while
massive
investigations
disclosed
potentials
precisely
synthesized
polymers,
researchers
made
considerable
efforts
approach
well-defined
fluorinated
copolymers.
This
minireview
discusses
challenges
controlled
radical
copolymerizations
(CRCPs)
fluoroalkenes
provides
a
concise
perspective
on
recent
progress
CRCPs
(e.g.,
tetrafluoroethylene,
chlorotrifluoroethylene,
hexafluoropropene,
perfluoroalkyl
vinyl
ethers)
with
non-fluorinated
comonomers,
which
enabled
on-demand
preparations
various
main-chain
predefined
molar
masses,
low
dispersities,
as
well
regulable
chemical
compositions
sequences.
The
synthetic
advantages
will
promote
facile
access
customized
for
high-tech
such
batteries,
coatings
so
on.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(34), P. 15413 - 15430
Published: July 26, 2022
Since
its
inception,
atom
transfer
radical
polymerization
(ATRP)
has
seen
continuous
evolution
in
terms
of
the
design
catalyst
and
reaction
conditions;
today,
it
is
one
most
useful
techniques
to
prepare
well-defined
polymers
as
well
notable
examples
catalysis
polymer
chemistry.
This
Perspective
highlights
fundamental
advances
ATRP
reactions
catalysts,
focusing
on
crucial
role
that
mechanistic
studies
play
understanding,
rationalizing,
predicting
outcomes.
A
critical
summary
traditional
systems
provided
first;
we
then
focus
recent
developments
improve
selectivity,
control
polymerizations
via
external
stimuli,
employ
new
photochemical
or
dual
catalytic
with
an
outlook
future
research
directions
open
challenges.
Chemical Society Reviews,
Journal Year:
2023,
Volume and Issue:
52(9), P. 3035 - 3097
Published: Jan. 1, 2023
In
this
review,
we
provide
a
brief
history,
progress,
and
applications,
discuss
the
remaining
challenges
of
photocontrolled
reversible
addition-fragmentation
chain
transfer
(RAFT)
polymerization
(i.e.,
photoinduced
electron/energy
transfer-RAFT
(PET-RAFT),
photoiniferter,
photomediated
cationic
RAFT
polymerization).
Among
these,
visible-light-driven
has
attracted
particular
attention
in
recent
years
due
to
its
benefits,
including
low
energy
consumption
safe
reaction
procedure.
Moreover,
incorporation
visible-light
photocatalysis
conferred
attractive
features,
such
as
spatiotemporal
control
oxygen
tolerance;
however,
clear
understanding
mechanism
not
been
completely
provided.
We
also
present
research
efforts
elucidate
mechanisms
with
aid
quantum
chemical
calculations
combined
experimental
evidence.
This
review
offers
an
insight
into
better
design
systems
for
desired
applications
helps
realize
full
potential
both
academic-
industrial-scale
applications.
Chemical Science,
Journal Year:
2022,
Volume and Issue:
13(39), P. 11540 - 11550
Published: Jan. 1, 2022
Photoinduced
atom
transfer
radical
polymerization
(photo-ATRP)
has
risen
to
the
forefront
of
modern
polymer
chemistry
as
a
powerful
tool
giving
access
well-defined
materials
with
complex
architecture.
However,
most
photo-ATRP
systems
can
only
generate
radicals
under
biocidal
UV
light
and
are
oxygen-sensitive,
hindering
their
practical
use
in
synthesis
biohybrids.
Herein,
inspired
by
photoinduced
electron
transfer-reversible
addition-fragmentation
chain
(PET-RAFT)
polymerization,
we
demonstrate
dual
photoredox/copper
catalysis
that
allows
open-air
ATRP
green
irradiation.
Eosin
Y
was
used
an
organic
photoredox
catalyst
(PC)
combination
copper
(X-Cu
Nature Communications,
Journal Year:
2023,
Volume and Issue:
14(1)
Published: Jan. 6, 2023
Cyanoarene-based
photocatalysts
(PCs)
have
attracted
significant
interest
owing
to
their
superior
catalytic
performance
for
radical
anion
mediated
photoredox
catalysis.
However,
the
factors
affecting
formation
and
degradation
of
cyanoarene-based
PC
(PC•‒)
are
still
insufficiently
understood.
Herein,
we
therefore
investigate
PC•‒
under
widely-used
photoredox-mediated
reaction
conditions.
By
screening
various
PCs,
elucidate
strategies
efficiently
generate
with
adequate
excited-state
reduction
potentials
(Ered*)
via
supra-efficient
generation
long-lived
triplet
excited
states
(T1).
To
thoroughly
behavior
in
actual
reactions,
a
reductive
dehalogenation
is
carried
out
as
model
identified
dominant
photodegradation
pathways
PC•‒.
Dehalogenation
coexistent
depending
on
rate
electron
transfer
(ET)
substrate
strongly
depends
electronic
steric
properties
PCs.
Based
understanding
both
PC•‒,
demonstrate
that
efficient
highly
reducing
allows
catalyzed
aryl/alkyl
halides
at
loading
low
0.001
mol%
high
oxygen
tolerance.
The
present
work
provides
new
insights
into
reactions
reactions.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(44), P. 24315 - 24327
Published: Oct. 25, 2023
Photoinduced
reversible-deactivation
radical
polymerization
(photo-RDRP)
techniques
offer
exceptional
control
over
polymerization,
providing
access
to
well-defined
polymers
and
hybrid
materials
with
complex
architectures.
However,
most
photo-RDRP
methods
rely
on
UV/visible
light
or
photoredox
catalysts
(PCs),
which
require
multistep
synthesis.
Herein,
we
present
the
first
example
of
fully
oxygen-tolerant
red/NIR-light-mediated
photoinduced
atom
transfer
(photo-ATRP)
in
a
high-throughput
manner
under
biologically
relevant
conditions.
The
method
uses
commercially
available
methylene
blue
(MB+)
as
PC
[X-CuII/TPMA]+
(TPMA
=
tris(2-pyridylmethyl)amine)
deactivator.
mechanistic
study
revealed
that
MB+
undergoes
reductive
quenching
cycle
presence
TPMA
ligand
used
excess.
formed
semireduced
MB
(MB•)
sustains
by
regenerating
[CuI/TPMA]+
activator
together
provides
polymerization.
This
dual
catalytic
system
exhibited
excellent
oxygen
tolerance,
enabling
polymerizations
high
monomer
conversions
(>90%)
less
than
60
min
at
low
volumes
(50-250
μL)
synthesis
library
DNA-polymer
bioconjugates
narrow
molecular
weight
distributions
(Đ
<
1.30)
an
open-air
96-well
plate.
In
addition,
broad
absorption
spectrum
allowed
ATRP
be
triggered
UV
NIR
irradiation
(395-730
nm).
opens
avenues
for
integration
orthogonal
reactions.
Finally,
MB+/Cu
catalysis
showed
good
biocompatibility
during
cells,
expands
potential
applications
this
method.
Chemical Society Reviews,
Journal Year:
2024,
Volume and Issue:
53(7), P. 3384 - 3456
Published: Jan. 1, 2024
The
scientific
community
has
witnessed
extensive
developments
and
applications
of
organoboron
compounds
as
synthetic
elements
metal-free
catalysts
for
the
construction
small
molecules,
macromolecules,
functional
materials
over
last
two
decades.
This
review
highlights
achievements
organoboron-mediated
polymerizations
in
past
several
decades
alongside
mechanisms
underlying
these
transformations
from
standpoint
polymerization
mode.
Emphasis
is
placed
on
free
radical
polymerization,
Lewis
pair
ionic
(cationic
anionic)
polyhomologation.
Herein,
alkylborane/O
European Polymer Journal,
Journal Year:
2024,
Volume and Issue:
211, P. 113001 - 113001
Published: March 30, 2024
Atom
transfer
radical
polymerization
(ATRP)
is
one
of
the
most
often
used
controlled
techniques.
It
employs
very
small
amounts
(ppm)
Cu
complexes
in
presence
various
chemical
reducing
agents
but
also
external
stimuli
such
as
light,
electrical
current
or
mechanical
forces.
can
be
carried
out
bulk,
solution,
and
dispersed
media.
ATRP
has
been
successfully
to
prepare
polymers
with
architecture
well-defined
topology,
composition,
functionality,
well
bioconjugates
organic–inorganic
hybrids.
This
article
summarizes
status
an
outlook
for
ATRP.
Langmuir,
Journal Year:
2024,
Volume and Issue:
40(11), P. 5571 - 5589
Published: March 5, 2024
Polymer
brushes
have
received
great
attention
in
recent
years
due
to
their
distinctive
properties
and
wide
range
of
applications.
The
synthesis
polymer
typically
employs
surface-initiated
atom
transfer
radical
polymerization
(SI-ATRP)
techniques.
To
realize
the
control
process
different
environments,
various
SI-ATRP
techniques
triggered
by
stimuli
been
developed.
This
review
focuses
on
latest
developments
stimuli-triggered
methods,
such
as
electrochemically
mediated,
photoinduced,
enzyme-assisted,
mechanically
controlled,
organocatalyzed
ATRP.
Additionally,
technology
a
combination
multiple
sources
is
also
discussed.
Furthermore,
applications
lubrication,
biological
applications,
antifouling,
catalysis
are
systematically
summarized
Despite
advancements
types
1D,
2D,
3D
via
controlled
polymerization,
contemporary
challenges
remain
quest
for
more
efficient
straightforward
synthetic
protocols
that
allow
precise
over
composition,
structure,
functionality
brushes.
We
anticipate
readers
could
promote
understanding
surface
functionalization
based
ATRP-mediated
envision
future
directions
application
coating
technologies.
