Angewandte Chemie,
Год журнала:
2024,
Номер
137(1)
Опубликована: Окт. 24, 2024
Abstract
Heterometallic
cluster‐based
materials
offer
the
potential
to
incorporate
multiple
functionalities,
leveraging
aggregation
effects
of
clusters
and
translating
this
heterogeneity
complexity
into
unexpected
properties
that
are
more
than
just
sum
their
components.
However,
rational
construction
heterometallic
remains
challenging
due
metal
cation
coordination
structural
unpredictability.
This
minireview
provides
insights
a
general
synthetic
strategy
based
on
Hard
Soft
Acids
Bases
(HSAB)
theory,
summarizing
its
advantages
in
designed
synthesis
discrete
(intracluster
assembly)
infinite
(intercluster
assembly).
Furthermore,
it
emphasizes
exploit
intrinsic
mixed
components
achieve
breakthroughs
across
broad
range
applications.
The
from
review
expected
drive
progress
controllable
predictable
manner.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
64(1)
Опубликована: Окт. 24, 2024
Heterometallic
cluster-based
materials
offer
the
potential
to
incorporate
multiple
functionalities,
leveraging
aggregation
effects
of
clusters
and
translating
this
heterogeneity
complexity
into
unexpected
properties
that
are
more
than
just
sum
their
components.
However,
rational
construction
heterometallic
remains
challenging
due
metal
cation
coordination
structural
unpredictability.
This
minireview
provides
insights
a
general
synthetic
strategy
based
on
Hard
Soft
Acids
Bases
(HSAB)
theory,
summarizing
its
advantages
in
designed
synthesis
discrete
(intracluster
assembly)
infinite
(intercluster
assembly).
Furthermore,
it
emphasizes
exploit
intrinsic
mixed
components
achieve
breakthroughs
across
broad
range
applications.
The
from
review
expected
drive
progress
controllable
predictable
manner.
Inorganic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 6, 2025
Herein,
we
report
the
Ca@Pb12
cluster,
an
all-main-group-metal
endofullerene
possessing
highly
symmetric
icosahedral
(Ih)
Platonic
solid
structure.
The
endohedral
environment
endows
Ca
atom
with
concrete
transition-metal-like
bonding
behaviors,
as
evidenced
by
18e
(in
3d104s24p6
configuration)
valence
shell
structure
and
five
strong
Pb12
→
Ca(3d)
dative
bonds,
whose
orbital
interaction
energy
(ΔEorb,
-134.2
kcal/mol)
represents
54.9%
of
total
ΔEorb
(-244.4
between
Ca2+
[Pb12]2-.
Moreover,
since
favorable
interactions
can
compensate
for
enlarged
steric
repulsion
during
encapsulation,
is
thermodynamically
stable,
dynamically
rigid
(up
to
1300
K),
electronically
robust,
verified
large
HOMO-LUMO
gaps
(4.58
eV),
high
vertical
detachment
(6.39
low
electron
affinity
(-0.71
eV).
It
first
viable
endofullerene,
where
guest
alkaline
earth
metal
exhibits
typical
behaviors
transition
metals.
Inorganic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 7, 2025
Heterometallic
3d-4f
cluster
complexes
have
enjoyed
much
recent
interest
because
of
their
structural
esthetics,
unique
properties,
and
useful
applications.
A
the
formula
[Gd68Co60(OH)116(CH3COO)8(IDA)56(CO3)4(C2O4)8(H2O)92Cl16]Cl48·10H2O·60CH3OH
(Gd68Co60,
IDA:
iminodiacetate),
obtained
by
cohydrolysis
Gd3+
Co2+
in
presence
IDA,
is
herein
reported.
Crystallographic
studies
revealed
its
saddle-shaped
cyclic
structure
featuring
a
nanometer-sized
central
cavity.
maximum
magnetic
entropy
change
38.58
J·K-1·kg-1
was
achieved
at
3.0
K
7.0
T,
placing
Gd68Co60
favorably
alongside
better-performing
clusters
for
cooling
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 6, 2025
Developing
high-performance
adsorbents
for
iodine
uptake
and
storage
has
become
an
urgent
priority
safe
disposal
long-term
of
nuclear
waste.
In
this
work,
two
cyclic
lanthanide-aluminum
clusters
with
the
formula
[Ln12Al72(hmp)60(C2H5O2)6(μ2-OH)120(μ3-OH)18(H2O)30]Cl24·(NO3)24·(H2O)x
(Ln
=
Tb,
x
≈
80,
Tb12Al72;
Ln
Gd,
100,
Gd12Al72;
Hhmp
2-(hydroxymethyl)pyridine
C2H6O2
ethylene
glycol)
are
reported.
Single-crystal
analysis
reveals
that
its
inner
diameter
is
approximately
1.1
nm,
outer
4.1
nm
a
thickness
3.1
nm.
The
packing
through
intermolecular
interactions
generates
3D
supramolecular
structure
one-dimensional
channels.
Investigation
adsorption
performance
cluster
indicates
capacity
3.14
g
g-1
Tb12Al72
Gd12Al72.
effectiveness
largely
due
to
accessible
micropore
along
high
density
pyridine
rings
abundant
hydroxyl
oxygen
atoms.
Consistently,
DFT
calculations
indicate
[Al(μ-OH)n]
ring
regions
synergistically
facilitate
adsorption,
effectively
promoting
dissociation
I2
into
I-
anions.
This
unique
environment
enhances
electrostatic
stabilization
polyiodide
anions
strong
Coulombic
attraction,
significantly
boosting
capture
iodine.
Inorganic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 18, 2025
In
this
paper,
a
polynuclear
heterometallic
compound
(H3O)[Al3Ni4(OH)6(MBA-NO2)6(H2O)6]
(Al3Ni4,
H2MBA-NO2
=
2-hydroxy-3-methoxy-5-nitrobenzoic
acid)
with
seven-star
disk
metal
core
has
been
synthesized
by
the
solvothermal
method.
Al3Ni4
good
stability
in
water
and
several
organic
solvents,
its
solid
powder
shows
photothermal
effect
under
980
nm
laser
irradiation,
temperature
can
reach
138.8
°C
within
100
s
1.0
W
cm-2
power
irradiation.
Considering
effect,
evaporation
of
was
measured.
It
be
further
used
as
material
seawater
evaporation.
Accounts of Chemical Research,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 29, 2025
ConspectusAtomically
precise
metal
clusters
with
well-defined
crystal
structures
have
emerged
as
a
rapidly
growing
field
within
coordination
and
materials
chemistry.
Among
them,
lanthanide-containing
(LCCs)
are
particularly
notable
for
their
aesthetically
pleasing
architectures
intriguing
properties.
Achieving
synthesis
accurate
structural
characterization
of
these
is
crucial
unlocking
potential
applications.
Mass
spectrometry
(MS),
electrospray
ionization
mass
(ESI-MS),
has
proven
to
be
powerful
tool,
providing
exceptional
sensitivity
clarity
in
revealing
the
formation
mechanisms
details
clusters.
In
this
Account,
we
explore
synthesis,
characterization,
assembly
LCCs
utilizing
ESI-MS.
We
begin
by
tracing
historical
development
LCCs,
emphasizing
critical
role
single-crystal
X-ray
diffraction
confirmation
challenges
associated
it.
then
discuss
application
ESI-MS
characterizing
highlighting
how
technique
can
monitor
processes
determine
molecular
weights
charge
states.
introduce
difference
fingerprint
isomorphism
(MDFI)
method,
which
facilitate
rapid
analysis
LCCs'
data.
Furthermore,
state
solution
characterization.
By
ESI-MS,
enhance
understanding
propose
new
strategies
designing
synthesizing
tailored
functions.
Looking
forward,
method
will
play
increasingly
significant
roles
LCC
research.
The
continued
technologies
deepen
structure-property
relationships.
With
ongoing
convergence
computational
chemistry
information
science,
anticipate
more
design
leading
broader
applications
magnetism,
optics,
catalysis.
