Molecular Design Principles for Photoactive Transition Metal Complexes: A Guide for “Photo-Motivated” Chemists
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 27, 2025
Luminescence
and
photochemistry
involve
electronically
excited
states
that
are
inherently
unstable
therefore
spontaneously
decay
to
electronic
ground
states,
in
most
cases
by
nonradiative
energy
release
generates
heat.
This
dissipation
can
occur
on
a
time
scale
of
100
fs
(∼10–13
s)
usually
needs
be
slowed
down
at
least
the
nanosecond
(∼10–9
for
luminescence
intermolecular
occur.
is
challenging
task
with
many
different
factors
consider.
An
alternative
emerging
strategy
target
dissociative
lead
metal–ligand
bond
homolysis
subnanosecond
access
synthetically
useful
radicals.
Based
thorough
review
recent
advances
field,
this
article
aims
provide
concise
guide
obtaining
luminescent
photochemically
coordination
compounds
d-block
elements.
We
hope
encourage
"photo-motivated"
chemists
who
have
been
reluctant
apply
their
synthetic
other
knowledge
photophysics
photochemistry,
we
intend
stimulate
new
approaches
control
state
behavior.
Language: Английский
Fine-Tuning the Excited-State Dynamics of Heteroleptic Ruthenium(II) Polypyridyl Complexes with Systematic Variation of Benzazole-Substituted 8-Hydroxyquinolines
Inorganic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 30, 2025
A
series
of
structurally
related
bistridentate
heteroleptic
Ru(II)
polypyridyl
complexes,
[RuII(ttpy)(8-HQLS/N/O)]+
(Ru1-Ru3),
were
synthesized,
where
ttpy
=
p-tolyl
terpyridine
and
8-HQLS/N/O
are
monoanionic
N^N^O-donor
tridentate
ligands
(8-HQLX),
derived
from
8-hydroxyquinoline
(8-HQ),
namely,
8-HQLS
2-(2'-benzothiazole)-8-hydroxyquinoline,
8-HQLN
2-(2'-benzimidazole)-8-hydroxyquinoline,
8-HQLO
2-(2'-benzoxazole)-8-hydroxyquinoline.
The
electronic
structures
these
rigid
systematically
tuned
by
varying
the
noncoordinating
heteroatoms
(S,
O,
NH)
in
five-membered
heterocyclic
ring,
impacting
properties,
redox
potentials,
excited-state
lifetime/dynamics,
deactivation
pathways
photophysical
behavior
corresponding
complexes.
Notably,
[RuII(ttpy)(8HQLN)]+
(Ru2)
exhibited
an
lifetime
(τ
>
1
ns
CH3CN
at
RT)
surpassing
that
homoleptic
complex
[Ru(ttpy)2]2+
∼
0.62
ns),
despite
its
more
distorted
octahedral
geometry.
These
complexes
(Ru1-Ru3)
showed
extended
lifetimes
compared
to
their
counterpart
Ru4.
displayed
absorption
red
region,
which
is
favorable
for
phototherapeutic
applications.
Their
relative
singlet
oxygen
(1O2)
quantum
yields
(ΦΔ)
ranged
0.03
0.10.
Given
reasonable
1O2
generation
ability,
demonstrated
potential
as
photocatalysts
organic
substrates,
evidenced
effectiveness
photooxidation
PPh3
Ph3P=O
a
model
reaction.
Language: Английский
Wearable devices for monitoring sweat glucose: an integrated strategy for efficient electrochemical sensors
Sensors and Actuators Reports,
Journal Year:
2025,
Volume and Issue:
9, P. 100339 - 100339
Published: May 21, 2025
Language: Английский
Sterically Induced Acceleration of Aryl Halide Activation by Pd(0): A Radical Alternative to 2-Electron Oxidative Addition
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: May 29, 2025
The
first
elementary
step
of
Pd(0)-catalyzed
cross-coupling
involves
the
activation
an
aryl
halide
by
a
Pd(0)
catalyst,
which
is
widely
assumed
to
proceed
in
formal
2-electron
process,
involving
concerted
cleavage
bond
and
formation
aryl-Pd
as
generate
Pd(II)
complex.
Contrary
common
reactivity
assumptions
under
this
mechanistic
manifold,
we
observed
that
severe
steric
hindrance
catalyst
did
not
inhibit
thermal
but
instead
greatly
accelerated
it,
giving
full
conversion
ortho,ortho-di-tert-butyl-substituted
bromide
1
min
at
room
temperature
on
gram
scale
with
bulky
catalyst.
Our
data
revealed
1-electron-based
halogen
abstraction
operative
such
sterically
demanding
settings.
Language: Английский