Exploring the Potential of Al(III) Photosensitizers for Energy Transfer Reactions
Inorganic Chemistry,
Journal Year:
2024,
Volume and Issue:
63(34), P. 15829 - 15840
Published: Aug. 12, 2024
Three
homoleptic
Al(III)
complexes
(Al1–Al3)
with
different
degrees
of
methylation
at
the
2-pyridylpyrrolide
ligand
were
systematically
tested
for
their
function
as
photosensitizers
(PS)
in
two
types
energy
transfer
reactions.
First,
generation
reactive
singlet
oxygen
(1O2),
and
second,
isomerization
(E)-
to
(Z)-stilbene.
1O2
was
directly
evidenced
by
its
characteristic
NIR
emission
around
1276
nm
indirectly
reaction
an
organic
substrate
[e.g.
2,5-diphenylfuran
(DPF)]
using
situ
UV/vis
spectroscopy.
In
a
previous
study,
presence
additional
methyl
groups
found
be
beneficial
photocatalytic
reduction
CO2
CO,
but
here
Al1
without
any
exhibits
superior
performance.
To
rationalize
this
behavior,
combination
photophysical
experiments
(absorption,
excited
state
lifetimes)
together
photostability
measurements
scalar-relativistic
time-dependent
density
functional
theory
calculations
applied.
As
result,
exhibited
highest
quantum
yield
(64%),
longest
lifetime
(8.7
ns)
best
under
conditions
required
reactions
(e.g.
aerated
chloroform).
Moreover,
provided
rate
constant
(0.043
min–1)
oxygenation
DPF,
outperforming
even
noble
metal-based
competitors
such
[Ru(bpy)3]2+.
Finally,
enabled
long-term
test
(7
h),
which
successfully
recycled
seven
times,
underlining
high
potential
new
class
earth-abundant
PSs.
Language: Английский
Corrolato(oxo)antimony(V) Dimer with Hydrogen-Bond Donor Groups in Secondary Coordination Sphere as a Catalyst for Hydrogen Evolution Reaction
Inorganic Chemistry,
Journal Year:
2024,
Volume and Issue:
63(45), P. 21462 - 21473
Published: Oct. 28, 2024
The
focus
is
on
developing
alternative
molecular
catalysts
using
main-group
elements
and
implementing
strategic
improvements
for
sustainable
hydrogen
production.
For
this
purpose,
a
FB
corrole
with
(2-(2-((4-methylphenyl)sulfonamido)ethoxy)phenyl)
group
inserted
into
the
meso
position
(C-10)
of
corrole,
along
its
high-valent
(corrolato)(oxo)antimony(V)
dimer,
was
synthesized.
In
crystal
structure
analysis
dimer
complex,
it
noted
that
sulfonamido
in
ligand
periphery
sits
atop
ring.
electrochemical
evolution
reaction
(HER)
studied
compared
previously
reported
which
lacks
hydrogen-bond
donor
groups
secondary
coordination
sphere.
newly
designed
molecules,
featuring
sphere,
demonstrated
clear
superiority
HER.
Controlled
potential
electrolysis
employed
to
evaluate
charge
accumulation
associated
generation
homogeneous
three-electrode
system
presence
50
mM
TFA.
produced
exhibits
Faradaic
efficiency
approximately
80.96%,
turnover
frequency
(TOF)
0.44
h–1,
production
rate
52.83
μL
highlighting
effective
catalytic
activity
evolution.
Language: Английский