Polyoxometalates,
Journal Year:
2024,
Volume and Issue:
4(1), P. 9140081 - 9140081
Published: Oct. 10, 2024
The
supramolecular
assembly
of
a
series
covalently
modified
Anderson-type
polyoxometalates
(POMs)
and
18-crown-6
ethers
has
been
investigated
for
the
first
time.
Seven
new
POM-crown
ether
complexes
are
prepared
by
varying
countercations
modification
modes
Anderson
clusters,
fully
characterized
single-crystal
X-ray
diffraction,
ESI-TOF-MS,
1H-NMR
etc.
It
is
demonstrated
that
alkali
metal
cations
residing
in
cavity
crown
served
as
super-cations
to
bind
POM
hybrids,
thereby
generating
assemblies
with
different
architectures
compositions.
More
interestingly,
five
out
seven
show
novel
pseudo-rotaxane
structures,
which
obtained
changing
clusters
from
symmetric
asymmetric
ones.
These
pseudo-rotaxanes
have
not
reported
previously,
considered
an
effective
pathway
construct
POM-based
complementary
structural
chemical
properties.
Inorganic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 15, 2025
Developing
new
photocatalysts
for
the
selective
oxidation
of
thioethers
to
high-value-added
sulfoxides
under
low-oxygen
mild
conditions
is
a
promising
but
challenging
strategy.
Here,
polyoxometalate-based
metal–organic
framework
(POMOF),
CoBW12–TPT,
was
successfully
synthesized,
wherein
continuous
π···π
stacking
interactions
and
direct
coordination
bonds
not
only
strengthen
framework's
stability
also
accelerate
electron
transfer.
A
series
experiments
theoretical
studies,
including
control
experiments,
kinetic
electrochemical
spectroscopic
analyses,
paramagnetic
resonance,
revealed
synergistic
catalytic
effect
among
Co(II)
metal
centers,
BW12O405–,
photosensitizer
TPT.
CoBW12–TPT
applied
in
photocatalytic
sulfoxides.
Under
irradiation,
photoinduced
transfer
POMOF
leads
generation
superoxide
radicals
from
O2,
which
controls
sulfoxide
compounds
desulfurization
reaction
shows
good
activity.
In
particular,
it
can
be
construction
some
drug
molecules
such
as
Modafinil
Albendazole
Oxide.
Inorganic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 14, 2025
Three
cases
of
aminobenzoic
acid
hybrid
polyoxotungstates,
Na3(H3O)2[(HPW6O21)
(O2CC6H4NH2)3]·7H2O
(1),
K2(H3O)4[(AsW6O21)(O2CC6H4NH2)3]·4H2O
(2),
and
[(H2N(CH3)2]3Na2(H3O)[(SbW6O21)
(3),
were
successfully
synthesized.
This
is
the
first
report
successful
assembly
hexanuclear
{XW6}
(X
=
HPIII,
AsIII,
or
SbIII)
clusters
organic
carboxylic
(para
acid)
ligands.
All
three
hybrids
feature
a
common
unit
composed
six-membered
{WO6}
octahedral
ring
capped
by
one
{XO3}
trigonal
pyramid.
Furthermore,
these
possess
an
extensive
three-dimensional
network
hydrogen
bonds,
which
not
only
provide
high
thermal
stability
but
also
contribute
to
excellent
proton
conductive
performances.
Simultaneously,
based
on
Hirshfeld
partition
analysis,
combined
with
interaction
between
POMs
water
molecules,
transport
mechanisms
highlighted.
Inorganic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 12, 2025
The
photocatalytic
recovery
of
noble
metals
on
photosensitive
semiconductors
such
as
TiO2
is
well-established
for
forming
M/TiO2
but
has
notable
drawbacks.
suffers
from
low
conversion
efficiency
due
to
significant
recombination
photogenerated
electron–hole
pairs.
Its
wide
energy
band
gap
(3.2
eV)
also
restricts
excitation
high-energy
UV
light,
limiting
its
use
with
solar
energy.
This
study
proposes
an
efficient
alternative
using
hybrid
polyoxometalate
(POM)–porphyrin
copolymers
the
Ag
and
Pt
under
visible
light.
Copolymeric
films
composed
polyoxometalates
porphyrins
have
been
obtained
by
electrooxidation
5,15-(di-p-tolyl)porphyrin
(H2T2P)
or
2,3,7,8,12,13,17,18-octaethylporphine
zinc(II)
(ZnOEP)
together
Keggin
Wells–Dawson-type
organosilyl
polyoxophosphotungstate
([PW11Si2O40C26H16N2]TBA3
[P2W17Si2O62C26H16N2]TBA6).
In
these
films,
porphyrin
subunits
can
be
excited
illumination,
acting
photosensitizers
that
transfer
electrons
catalysts.
Notably,
POM–porphyrin
demonstrated
high
in
Pt(IV)
photoreduction
over
repeated
cycles
without
catalyst
degradation.
Inorganic Chemistry,
Journal Year:
2025,
Volume and Issue:
64(1), P. 443 - 451
Published: Jan. 2, 2025
Proton
exchange
membrane
fuel
cells
(PEMFCs)
are
developing
into
very
meaningful
clean
energy
to
fundamentally
address
environmental
pollution.
Among
which
the
most
studied
Nafion
series
membranes
limited
under
large-scale
use,
and
some
strong
oxidizing
groups
such
as
hydrogen
peroxide
will
attack
structure
of
Nafion,
shortening
lifespan
PEMFCs.
Therefore,
it
is
crucial
develop
a
proton-conductive
material
with
stability
broad
application.
In
this
study,
novel
hourglass-type
P4Mo6-based
POMOFs
denoted
(H2timb)2[Mn3(H3P4Mo6O31)2]·4H2O
was
synthesized
using
1,3,5-tri(1H-imidazole-1-yl)benzene
(timb)
ligand.
It
found
that
CUST-577
exhibited
an
excellent
proton
conductivity
8.9
×
10–3
S
cm–1
at
80
°C
98%
RH
(relative
humidity),
proving
conducted
by
protons.
addition,
also
had
greater
H2O2
decomposition
ability,
thereby
improving
longevity
cells.
three-electrode
system,
displayed
specific
capacitance
(Cs)
value
308
F
g–1
current
density
0.15
A
g–1,
retention
88.3%
after
2000
cycles.
Since
electrolyte
can
deliver
protons
for
redox
reaction
various
pseudocapacitor
(PC)
electrode
materials,
may
be
promising
polyacid-based
conductor
PC
material.
Inorganic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 6, 2025
Three
distinct
polyoxovanadoborates
modified
by
transition
metals,
specifically
{V10B26Cd8(phen)12}
(1,
phen
=
1,10-phenanthroline),
{V10B32Zn6}
(2),
and
{V12B32Cu2}
(3),
have
been
synthesized
under
hydrothermal
conditions.
Compounds
1-3
feature
three
unique
sandwich-type
clusters,
namely,
{V10B24},
{V10B28},
{V12B32},
each
characterized
toroidal
(O═VO2)n
(n
10,
12)
rings.
In
the
structure
of
1,
two
pairs
{Cd(phen)}
{Cd(phen)2}
units
are
grafted
on
{B13}
rings
from
top
bottom
{V10B24}
cluster,
respectively.
Compound
2
is
a
1D
polymeric
chain
consisting
bridging
ligand
{ZnO6}
unit
linked
to
which
accommodates
{Zn4B4O8}
unit.
The
{V12B32}
cluster
in
3
interconnected
with
[Cu(en)2]2+
(en
ethylenediamine)
create
sql
layer,
further
stacked
an
ABAB
sequence
form
3D
supramolecular
framework.
Additionally,
sulfide
catalytic
oxidation
experiments
revealed
that
compound
efficient
stable
catalyst.
