Journal of Sulfur Chemistry,
Год журнала:
2023,
Номер
45(2), С. 184 - 197
Опубликована: Ноя. 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,
Год журнала:
2024,
Номер
63(19), С. 8739 - 8749
Опубликована: Май 2, 2024
Ground-state
and
time-dependent
density
functional
theory
(TDDFT)
calculations
with
the
long-range-corrected,
Coulomb-attenuating
CAMY-B3LYP
exchange-correlation
large,
all-electron
STO-TZ2P
basis
sets
have
been
used
to
examine
potential
"inverse
hypercorrole"
character
of
meso-p-nitrophenyl-appended
dicyanidocobalt(III)
corrole
dianions.
The
effect
is
most
dramatic
for
5,15-bis(p-nitrophenyl)
derivatives,
where
it
manifests
itself
in
intense
NIR
absorptions.
10-aryl
groups
these
complexes
play
a
modulatory
role,
as
evinced
by
experimental
UV–visible
spectroscopic
electrochemical
data
series
corroles.
TDDFT
(CAMY-B3LYP)
ascribe
features
clearly
transition
from
corrole's
a2u-like
HOMO
(retaining
D4h
irrep
metalloporphyrins)
nitrophenyl-based
LUMO.
outward
nature
this
contrasts
usual
phenyl-to-macrocycle
direction
charge
transfer
transitions
many
hyperporphyrins
hypercorroles;
thus,
studied
are
aptly
described
inverse
hypercorroles.
Inorganic Chemistry,
Год журнала:
2023,
Номер
62(49), С. 19956 - 19970
Опубликована: Ноя. 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,
Год журнала:
2024,
Номер
63(17), С. 7828 - 7837
Опубликована: Апрель 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,
Год журнала:
2024,
Номер
14(19), С. 5608 - 5615
Опубликована: Янв. 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,
Год журнала:
2024,
Номер
4(5), С. 485 - 491
Опубликована: Июнь 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,
Год журнала:
2024,
Номер
unknown
Опубликована: Янв. 1, 2024
The
recent
progress
regarding
the
synthesis
and
functionalization
of
formyl/acroleyl
substituted
corroles
their
reactivity
with
active
methylene
compounds
pyrroles
are
highlighted.
