Chemistry - A European Journal,
Год журнала:
2023,
Номер
29(64)
Опубликована: Сен. 7, 2023
Abstract
Alkylation
of
one
the
inner‐core
nitrogen
atoms
is
possible
approach
to
obtain
dianionic
corrole
ligands,
suitable
for
coordination
divalent
metal
ions,
such
as
Pd
II
.
Inner‐core
N‐methylation
can
be
obtained
by
treating
with
CH
3
I,
but
reaction
conditions
should
optimized
limit
formation
dimethylated
derivative.
Two
regioisomers,
N‐21
and
N‐22
methyl
derivatives
are
from
reaction,
first
product
achieved
in
a
higher
amount.
Structural
characterization
products
evidenced
distortion
induced
introduction
groups;
N
‐methylcorroles
chiral
compounds,
enantiomers
were
separated
chromatography,
their
absolute
configuration
assigned
ECD
computation.
Palladium
insertion
was
case
monosubstituted
corroles,
not
macrocycle;
X‐ray
complexes
showed
macrocycles.
The
do
show
luminescence
emission,
able
produce
singlet
oxygen
upon
irradiation.
also
inserted
human
serum
albumin
(HSA)
dispersed
water;
this
case,
protein
protects
corroles
photobleaching,
switch
type
I
mechanism
reactive
species
(ROS)
production
observed.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(23), С. 12429 - 12445
Опубликована: Май 31, 2023
The
renaissance
in
corrole
chemistry
is
strongly
correlated
with
synthetic
breakthroughs
that
started
1999,
regarding
the
one-pot
rather
than
multistep
syntheses
of
this
heme-like
N4
macrocycle.
This
largely
improved
accessibility
allowed
for
technological
advances
wherein
corresponding
metal
complexes
have
since
been
introduced
as
key
elements.
Great
emphasis
was
devoted
to
elucidation
unique
fundamental
features
distinguish
ligands,
among
them
outstanding
electron
donation
(σ
by
N
atoms
and
π
macrocycle)
transition
metals
chelated
them.
Such
investigations
remain
crucial
enabling
by-demand
tuning
metallocorrole
properties
distinctly
different
applications.
These
range
from
catalysis
organic
reactions,
through
bioimaging
disease
prevention/treatment
strategies,
photo-
electrocatalysis
clean
energy.
Surveyed
are
original
reports
impacted
these
developments,
together
some
most
recent
advances.
Inorganic Chemistry,
Год журнала:
2023,
Номер
62(13), С. 5292 - 5301
Опубликована: Март 23, 2023
Two
new
meso-substituted
oxido-molybdenum
corroles
were
synthesized
and
characterized
by
various
spectroscopic
techniques.
In
the
thermogram,
MoO[TTC]
(1)
exhibited
excellent
thermal
stability
up
to
491
°C
while
MoO[TNPC]
(2)
good
318
°C.
The
oxidation
states
of
molybdenum(V)
verified
electron
paramagnetic
resonance
(EPR)
spectroscopy
an
axial
compression
with
dxy1
configuration.
Oxido-molybdenum(V)
complexes
utilized
for
selective
epoxidation
olefins
high
TOF
values
(2066-3287
h-1)
in
yields
a
CH3CN/H2O
(3:2,
v/v)
mixture
presence
hydrogen
peroxide
as
green
oxidant
NaHCO3
promoter.
oxidative
bromination
catalytic
activity
oxido-molybdenum(V)
aqueous
medium
has
been
reported
first
time.
Surprisingly,
biomimics
vanadium
bromoperoxidase
(VBPO)
enzyme
remarkably
(36
988-61
646
p-cresol
other
phenol
derivatives.
Catalyst
higher
better
than
catalyst
due
electron-withdrawing
nitro
groups
evident
from
cyclic
voltammetric
studies.
Advanced Optical Materials,
Год журнала:
2024,
Номер
12(18)
Опубликована: Май 17, 2024
Abstract
The
intrinsic
quantum
nature
of
molecules
opens
exciting
opportunities
for
developing
the
field
information
science.
In
this
context,
porphyrins
stand
out
as
ideal
building
blocks
technologies
thanks
to
their
unique
optical
and
electrical
properties
well
capacity
accommodate
metal
atoms
ions.
This
review
bridges
chemistry
physics
porphyrins,
providing
an
overview
recent
advances
in
porphyrin‐based
molecular
qubits.
Starting
from
qubits,
explores
potential
porphyrin
units
combine,
leading
formation
logic
gates
hierarchical
higher‐dimensional
structures.
Next,
exploitation
porphyrins'
photophysical
realizing
long‐lived
high
spin
states
is
examined.
These
are
promising
photogeneration
multi‐level
systems
initialization
control
With
a
critical
eye
on
current
state‐of‐the‐art,
elucidates
future
perspectives
advancing
technologies.
Chemistry - A European Journal,
Год журнала:
2023,
Номер
29(41)
Опубликована: Май 3, 2023
Copper
and
silver
tritolylcorroles
(TTC)
are
symmetrically
functionalized
to
carry
two
tetracyanobutadiene
(TCBD)
entities
via
[2+2]
cycloaddition-retroeletrocyclization
reaction
involving
ethynyl
corroles
with
an
electron
acceptor,
tetracyanoethylene
(TCNE)
in
excellent
yields,
as
the
first
examples
of
corrole-TCBD
push-pull
systems.
The
strong
effect
resulted
charge
polarization
ground
state
resulting
a
considerable
hypsochromic
shift
spectrum
extending
it
into
near-IR
region.
Electrochemical
studies
coupled
computational
revealed
interactions
between
TCBD
corrole
π-system
degree
such
was
found
depend
on
metal
ion
present
cavity.
Energy
considerations
suggested
transfer
(CT)
from
S2
or
vibrationally
hot
S1
but
not
relaxed
case
CuTTC(TCBD)2
while
CT
occur
all
these
states
AgTTC(TCBD)2
.
Additionally,
high-energy
populate
low-lying
triplet
states.
Systematic
femtosecond
pump-probe
provided
ultimate
proof
for
occurrence
excited
function
excitation
wavelength
followed
by
efficient
population
study
brings
out
significance
efficiently
populating
rather
unusual
copper
carrying
entities.
Inorganic Chemistry,
Год журнала:
2023,
Номер
62(20), С. 7738 - 7752
Опубликована: Май 5, 2023
A
new
family
of
β-dicyanovinyl
(DCV)-appended
corroles
represented
as
MTPC(MN)
(where
M
=
3H,
Cu,
Ag,
and
Co(PPh3)
MN
malononitrile
TPC
5,10,15-triphenylcorrole)
were
synthesized
starting
from
the
free
base
mono
β-formyl
corrole,
H3TPC(CHO),
characterized
along
with
their
respective
MTPC(CHO)
MTPC
complexes
to
spectroscopic
electrochemical
properties
in
nonaqueous
media.
Comparisons
between
two
series
demonstrate
a
pronounced
substituent
effect
β-DCV
group
on
physicochemical
making
derivatives
substantially
easier
reduce
more
difficult
oxidize
than
formyl
or
unsubstituted
corroles.
In
addition,
colorimetric
spectral
detection
11
different
anions
(X)
form
tetrabutylammonium
salts
(TBAX,
X
PF6-,
OAc-,
H2PO4-,
CN-,
HSO4-,
NO3-,
ClO4-,
F-,
Cl-,
Br-,
I-)
also
investigated
Of
anions,
only
CN-
was
found
induce
changes
UV-vis
1H
NMR
spectra
metallocorroles.
This
data
revealed
that
CuTPC(MN)
AgTPC(MN)
act
chemodosimeters
for
selective
cyanide
ion
via
nucleophilic
attack
at
vinylic
carbon
DCV
substituent,
while
(PPh3)CoTPC(MN)
acts
chemosensor
sensing
axial
coordination
cobalt
metal
center.
low-limit
ions
observed
1.69
ppm
1.17
toluene.
