Journal of Sulfur Chemistry,
Journal Year:
2023,
Volume and Issue:
45(2), P. 184 - 197
Published: Nov. 8, 2023
A
facile
approach
for
the
syntheses
of
regioselective
meso-
mono,
di
(cis
and
trans),
tri
formylthien-2-ylporphyrins
from
meso-tetrathien-2-ylporphyrin
(ThP)
is
presented.
The
synthesized
mono
formylthien-2-ylporphyrin
ThP-CHO
was
further
functionalized
to
5-((5-terpyridinyl)thien-2-yl)-10,15,20-tris(thien-2-yl)porphyrin
(ThP-TPy)
Porphyrin-Corrole
(Por-Cor)
dyad.
influence
formyl
substitution
functionalization
on
thien-2-yl
ring(s)
with
porphyrin
central
π-system
examined
through
UV–Vis
absorption,
1H
NMR
spectroscopy
electrochemical
studies.
red
shift
Soret
band
Q
bands
in
absorption
spectrum
redox
potentials
are
shown
be
dependent
number
(ThP-CHO,
424
nm
<
ThPt-(CHO)2
ThPc-(CHO)2,
425
ThP(CHO)3,
427
nm).
significant
variation
distinct
bathochromic
series
derivatives,
ThP-TPy
Por-Cor
dyad
have
been
explained
based
near-planar
orientation
meso-thienyl
groups
core.
Inorganic Chemistry,
Journal Year:
2023,
Volume and Issue:
62(35), P. 14147 - 14151
Published: Aug. 24, 2023
Considering
the
worldwide
efforts
for
designing
catalysts
that
are
not
based
on
platinum
group
metals
while
still
reserving
many
advantages
thereof,
this
study
focused
variables
dictate
performance
of
cathodes
used
fuel
cells,
regarding
efficient
and
selective
reduction
oxygen
to
water.
This
was
done
by
investigating
two
kinds
porous
carbon
electrodes,
modified
molecular
cobalt(III)
complexes
chelated
corroles
differ
very
much
in
size
electron-withdrawing
capability.
Examination
electronic
effect
uncovered
shifts
CoII/CoIII
redox
potentials
also
large
differences
affinity
cobalt
center
external
ligands.
Spontaneous
absorption
found
depend
corrole's
substituents
(C6F5
≫
CF3
H)
metal's
axial
ligands
(PPh3
versus
pyridine),
as
well
porosity
electrodes
(BP2000
>
Vulcan).
The
better-performing
cobalt-based
were
almost
active
20%
Vulcan
terms
onset
potential
only
2-10%
undesirable
formation
hydrogen
peroxide.
Durability
addressed
using
best-performing
cathode
a
proper
anion-exchange
membrane
cell
setup,
revealing
little
voltage
change
during
12
h
operation.
Inorganic Chemistry,
Journal Year:
2023,
Volume and Issue:
62(49), P. 19956 - 19970
Published: Nov. 27, 2023
Four
new
β-functionalized
π-extended
cobalt
corroles
with
one
and
two
dicyanovinyl
(DCV)
or
dicyanobutadienyl
(DCBD)
moieties
at
the
3-
3,17-positions
have
been
synthesized
characterized
by
various
spectroscopic
techniques.
Interestingly,
DCV-
DCBD-appended
displayed
panchromatic
near-infrared
absorption
in
range
300–1100
nm
CH2Cl2
pyridine
solvents.
(MN)2-(Cor)Co
A2MN2-(Cor)Co
exhibited
8–9
times
enhancement
molar
absorptivity
of
Q
band
compared
to
parent
corrole
((Cor)Co).
The
unique
spectral
features
these
are
splitting,
broadening,
red-shifting
Soret
bands.
One
DCV
unit
brings
a
30–46
red
shift,
whereas
DCBD
40–75
shift
corresponding
precursors.
This
is
rare
that
intensity
longest
greater
than
equal
Soret-like
These
derivatives
exhibit
UV–vis
similar
those
chlorophyll
a.
A
220
mV
positive
per
group
160
were
observed
first
oxidation
potentials
(Cor)Co
desired
direction
for
utility
complexes
electrocatalysis.
DFT
studies
revealed
HOMO
LUMO
stabilized
after
appending
groups
on
macrocycle
“push–pull”
behavior
leading
promising
material
applications
nonlinear
optics
(NLO)
catalysis.
Inorganic Chemistry,
Journal Year:
2024,
Volume and Issue:
63(17), P. 7828 - 7837
Published: April 17, 2024
In
the
search
for
mild
agents
oxidative
cyclization
of
tetrapyrromethane
to
corresponding
corrole,
we
discovered
a
route
that
leads
monoazaporphyrin
with
three
meso-CF3
groups.
Optimization
studies
allowed
access
appreciable
amounts
this
new
macrocycle
paved
way
preparation
its
cobalt,
copper,
nickel,
zinc,
and
iron
complexes.
All
complexes
were
fully
characterized
by
various
spectroscopic
methods
X-ray
crystallography.
Their
photophysical
electrochemical
properties
determined
compared
those
analogous
porphyrins
in
order
deduce
effect
peripheral
N
atom.
Considering
global
efforts
designing
efficient
alternatives
platinum
group
metal
(PGM)
catalysts,
they
also
absorbed
onto
porous
carbon
electrode
material
studied
as
electrocatalysts
oxygen
reduction
reaction
(ORR).
The
cobalt
complex
was
found
be
operative
at
quite
positive
catalytic
onset
potential
good
selectivity
desirable
4-electrons/4-protons
pathway.
Catalysis Science & Technology,
Journal Year:
2024,
Volume and Issue:
14(19), P. 5608 - 5615
Published: Jan. 1, 2024
It
is
known
that
the
efficiency
of
hydrogen
evolution
reaction
(HER)
can
be
promoted
by
presence
proton
relay
groups
neighboring
a
catalytic
metal
center.
ACS Organic & Inorganic Au,
Journal Year:
2024,
Volume and Issue:
4(5), P. 485 - 491
Published: June 19, 2024
A
combined
direct
and
inverse
photoemission
study
of
coinage
metal
corroles
suggests
that
the
latter
technique,
in
favorable
cases,
can
provide
some
additional
information
relative
to
electrochemical
measurements.
Thus,
whereas
spectroscopy
(IPES)
provides
electron
affinities
for
addition
different
unoccupied
orbitals,
reduction
potentials
shed
light
on
energetics
successive
additions.
While
all
three
triphenylcorrole
(TPC)
complexes
exhibit
similar
ionization
potentials,
they
dramatically
spectra.
For
Cu[TPC],
lowest-energy
IPES
feature
(0.74
eV)
is
found
be
exceedingly
close
Fermi
level;
it
significantly
higher
Ag[TPC]
(1.65
much
Au[TPC]
(2.40
eV).
These
differences
qualitatively
mirror
those
observed
are
related
a
partially
metal-centered
LUMO
case
Cu-
fully
corrole-based
Au[TPC];
orbital
corresponds
LUMO+1
Ag[TPC].
Chemical Communications,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Jan. 1, 2024
The
recent
progress
regarding
the
synthesis
and
functionalization
of
formyl/acroleyl
substituted
corroles
their
reactivity
with
active
methylene
compounds
pyrroles
are
highlighted.
