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.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(14), С. 9506 - 9511
Опубликована: Апрель 1, 2024
Clusters
showing
a
giant
magnetocaloric
effect
(MCE)
are
of
interest
as
molecular
coolants
for
magnetic
refrigeration.
Herein,
we
report
two
heterometallic
clusters,
denoted
Gd152Ni14@Cl24
and
Sm152Ni8,
just
to
highlight
their
inorganic
core
motifs,
obtained
by
ligand-controlled
co-hydrolysis
Ni2+
Ln3+
(Ln
=
Gd,
Sm)
in
the
presence
N-(2-hydroxyethyl)iminodiacetic
acid
(H2HEIDA).
Both
clusters
display
fascinating
cubic
Tinkertoy-like
structures,
with
motifs
being
built
multiple
metallic
shells
Platonic
Archimedean
polyhedra.
The
isothermal
entropy
change─a
direct
measurement
MCE─was
determined
be
52.65
J·kg–1·K–1
at
2.5
K
7.0
T
Gd-containing
cluster;
this
value
is
highest
known
any
so
far
reported.
ACS Materials Letters,
Год журнала:
2024,
Номер
6(7), С. 2995 - 3006
Опубликована: Июнь 12, 2024
Atomically
precise
nanoclusters
(NCs),
which
bridge
the
gap
between
molecular
chemistry
and
nanochemistry,
are
drawing
significant
attention
in
various
fields.
Due
to
their
discrete
energy
structures
like
molecules,
NCs
exhibit
intriguing
optical
properties
defined
metal
sites,
making
them
an
ideal
platform
for
studying
photocatalytic
reactions.
This
perspective
elaborates
design
principles
efficient
based
water
splitting
photocatalysts
from
three
fundamental
aspects
photocatalysis:
(1)
light
absorption
charge
excitation,
(2)
separation
transport,
(3)
surface
An
outlook
on
future
work
developing
is
also
provided.
Atomically
precise
metal
nanoclusters
(MNCs)
represent
a
fascinating
class
of
ultrasmall
nanoparticles
with
molecule-like
properties,
bridging
conventional
metal-ligand
complexes
and
nanocrystals.
Despite
their
potential
for
various
applications,
synthesis
challenges
such
as
understanding
varied
synthetic
parameters
property-driven
persist,
hindering
full
exploitation
wider
application.
Incorporating
smart
methodologies,
including
closed-loop
framework
automation,
data
interpretation,
feedback
from
AI,
offers
promising
solutions
to
address
these
challenges.
In
this
perspective,
we
summarize
the
that
has
been
demonstrated
in
nanomaterials
explore
research
frontiers
MNCs.
Moreover,
perspectives
on
inherent
opportunities
MNCs
are
discussed,
aiming
provide
insights
directions
future
advancements
emerging
field
AI
Science,
while
integration
deep
learning
algorithms
stands
substantially
enrich
by
offering
enhanced
predictive
capabilities,
optimization
strategies,
control
mechanisms,
thereby
extending
MNC
synthesis.
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.
JACS Au,
Год журнала:
2024,
Номер
4(8), С. 3170 - 3182
Опубликована: Авг. 12, 2024
In
this
study,
we
present
the
first
example
of
using
a
machine
learning
(ML)-assisted
design
strategy
to
optimize
synthesis
formulation
enzyme/ZIFs
(zeolitic
imidazolate
framework)
for
enhanced
performance.
Glucose
oxidase
(GOx)
and
horseradish
peroxidase
(HRP)
were
chosen
as
model
enzymes,
while
Zn(eIM)2
(eIM
=
2-ethylimidazolate)
was
selected
ZIF
test
our
ML-assisted
workflow
paradigm.
Through
an
iterative
ML-driven
training-design-synthesis-measurement
workflow,
efficiently
discovered
GOx/ZIF
(G151)
HRP/ZIF
(H150)
with
their
overall
performance
index
(OPI)
values
(OPI
represents
product
encapsulation
efficiency
(E
in
%),
retained
enzymatic
activity
(A
thermal
stability
(T
%))
at
least
1.3
times
higher
than
those
systematic
seed
data
studies.
Furthermore,
advanced
statistical
methods
derived
from
trained
random
forest
qualitatively
quantitatively
reveal
relationship
among
synthesis,
structure,
enzyme/ZIF
system,
offering
valuable
guidance
future
studies
on
enzyme/ZIFs.
Overall,
proposed
holds
promise
accelerating
development
other
enzyme
immobilization
systems
biocatalysis
applications
beyond,
including
drug
delivery
sensing,
others.
Chinese Journal of Chemistry,
Год журнала:
2024,
Номер
unknown
Опубликована: Июнь 3, 2024
Comprehensive
Summary
The
precise
syntheses
of
transition–rare‐earth
metal
clusters
with
desired
structures
remain
a
great
challenge.
Herein,
by
utilizing
SO
4
2–
anion
released
in‐situ
decomposition
sodium
dodecyl
sulfate
(SDS)
as
template,
series
novel
high‐nuclearity
3d‐4f
clusters,
formulated
[Ni
24
Pr
22
(μ
3
‐OH)
31
(pida)
(SO
)
(NO
9
(CH
COO)
]·Br
·(NO
11
·16H
2
O·25CH
OH
(
1
,
H
pida
=
N
‐phenyliminodiacetic
acid),
Nd
·14H
O·24CH
and
Gd
36
(bida)
7
]·(SO
)·Br
·31H
O·32CH
bida
‐benzyliminodiacetic
have
been
successfully
isolated.
X‐ray
crystal
structure
analyses
reveal
that
all
the
cationic
{Ni
RE
}
cores
in
—
possess
ball‐like
C
v
symmetry,
can
be
viewed
consisting
an
inner
{RE
core
outer
shell.
From
to
due
lanthanide
contraction
effect,
coordination
numbers
for
rare‐earth
centers
are
different,
resulting
different
number
NO
–
anions
support
stabilize
skeleton
structures.
Meanwhile,
magnetic
properties
complexes
were
also
studied.
result
revealed
show
antiferromagnetic/ferrimagnetic
interactions,
exhibits
magneto‐caloric
effect
at
ultralow
temperatures
maximum
–Δ
S
m
(magnetic
entropy
change)
value
33.03
J·kg
−1
·K
3.0
K
T.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 5, 2025
Anions
are
important
as
templates
for
the
construction
of
many
structurally
sophisticated
and
functional
supramolecular
architectures.
Deciphering
specific
role
such
remains
a
great
challenge
due
to
unique
characteristics
anions.
Herein,
three
heterometallic
Ce–Ni
clusters,
namely,
[Ce24Ni36L36(μ4-OAc)6(OH)52(Cl)8]Cl6·110H2O
(Ce24Ni36,
OAc
=
acetate
ion,
L
N-methyliminodiacetate),
[Ce17Ni27L27(μ6-C2O4)6(OH)15(Cl)16(H2O)19](ClO4)2Cl6·45H2O
(Ce17Ni27),
[Ce21Ni30L30(μ6-C2O4)2(μ4-OAc)(OH)32(Cl)15(H2O)14](ClO4)4Cl7·55H2O
(Ce21Ni30),
were
obtained
characterized;
formation
these
cage-like
clusters
was
assisted,
respectively,
by
acetate,
oxalate,
combination
two
templates.
Structural
analyses
generate
key
information
on
anion-directed
hierarchical
assembly,
starting
from
primary
building
block
{CeNi3}
anion-specific
secondary
blocks
(SBUs)─the
tetragonal
{Ce4Ni8(OAc)}
pentagonal
{Ce5Ni9(C2O4)}.
Further
assembly
steps
guided
curved
SBUs,
affording
truncated
octahedral
Ce24Ni36
lantern-like
Ce17Ni27,
with
oxalate
being
sole
template,
respectively.
The
combined
use
produced
Ce21Ni30,
cluster
an
unprecedented
structure
viewable
hybrid
octahedron
dodecahedron.
