Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(29)
Published: May 7, 2024
Abstract
A
gold(I)‐cluster‐based
twin‐cage
has
been
constructed
by
post‐clustering
covalent
modification
of
a
hexa‐aldehyde
cluster
precursor
with
triaminotriethylamines.
The
cages‐on‐cluster
structure
double
cavities
and
four
binding
sites,
which
show
site‐discriminative
for
silver(I)
copper(I)
guests.
guests
in
the
tripodal
hats
affect
luminescence
cluster:
tetra‐silver(I)
host–guest
complex
is
weakly
red‐emissive,
while
bis‐copper(I)‐bis‐silver(I)
one
non‐emissive
but
stimuli‐responsive
supramolecule.
ion
inside
tri‐imine
cavity
oxidation
sensitive,
enables
release
bright
emissive
triggered
H
2
O
solution.
hybridization
to
construct
cluster‐based
cage
presents
an
innovative
concept
functional
design,
opens
up
new
avenues
finely
tuning
properties
clusters.
Chemical Reviews,
Journal Year:
2024,
Volume and Issue:
124(11), P. 7262 - 7378
Published: May 2, 2024
Ligand-protected
metal
clusters
possess
hybrid
properties
that
seamlessly
combine
an
inorganic
core
with
organic
ligand
shell,
imparting
them
exceptional
chemical
flexibility
and
unlocking
remarkable
application
potential
in
diverse
fields.
Leveraging
to
expand
the
library
of
available
materials
stimulate
development
new
functionalities
is
becoming
increasingly
pressing
requirement.
This
Review
focuses
on
origin
from
structural
analysis,
including
intra-cluster
bonding,
inter-cluster
interactions,
cluster-environments
metal-to-ligand
ratios,
thermodynamic
effects.
In
introduction,
we
briefly
outline
explain
differences
commonalities
M(I)/M(I/0)
coinage
clusters.
Additionally,
distinguish
bonding
characteristics
atoms
core,
which
give
rise
their
distinct
flexibility.
Section
2
delves
into
categories,
theories
related
following
sections
3
7,
primarily
elucidate
mechanisms
trigger
flexibility,
dynamic
processes
transformation,
resultant
alterations
structure,
ensuing
modifications
physical–chemical
properties.
8
presents
notable
applications
have
emerged
utilizing
assemblies.
Finally,
section
9,
discuss
future
challenges
opportunities
within
this
area.
ACS Materials Letters,
Journal Year:
2023,
Volume and Issue:
6(1), P. 281 - 289
Published: Dec. 19, 2023
Atomically
precise
copper
nanoclusters
have
recently
attracted
tremendous
attention,
as
they
often
exhibit
structures
and
properties
distinct
to
their
gold
silver
counterparts.
Although
considerable
progress
has
been
made
in
the
preparation
structure
determination
of
nanoclusters,
introduction
those
newly
created
materials
more
underlying
areas
such
nonlinear
optics
is
its
infancy.
Herein,
we
report
a
new
class
Cu50
exhibiting
tunable
optical
limiting
effect.
The
facile
prototype
reported
this
work
allows
discovery
up
four
clusters
with
nearly
identical
metal
framework,
namely,
Cu50(CF3COO)12(3,5-diMe-PhS)18(PPh3)4H2
(Cu50-1),
Cu50(CF3COO)10(4-F-PhS)20(PPh3)6H2
(Cu50-2),
Cu50(CF3COO)10(PhS)20(PPh3)6H2
(Cu50-3),
Cu50(PhCOO)10(4-F-PhS)20(PPh3)6H2
(Cu50-4).
molecular
series,
revealed
by
X-ray
single
crystal
analysis,
describes
stabilization
Cu44
core
an
organometallic
shell
thiolate-carboxylate-phosphine-copper.
combinatorial
studies
electrospray
ionization
mass
spectroscopy
(ESI-MS),
nuclear
magnetic
resonance
(NMR),
density
functional
theory
(DFT)
calculations
suggest
that
contain
18
free
valence
electrons,
making
them
probably
first
library
superatoms
featuring
18e.
As
nanosecond
Z-scan
measurements
results,
typical
effects,
indicating
promising
applications
field
(NLO).
More
importantly,
labile
surface
motifs
on
allow
us
tune
NLO
properties.
This
not
only
reports
atomically
process,
clear
structures,
but
also
encourages
research
exploration
exciting
areas.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(14), P. 9631 - 9639
Published: March 26, 2024
The
induced
structural
transformation
provides
an
efficient
way
to
precisely
modulate
the
fine
structures
and
corresponding
performance
of
gold
nanoclusters,
thus
constituting
one
important
research
topics
in
cluster
chemistry.
However,
driving
forces
mechanisms
these
processes
are
still
ambiguous
many
cases,
limiting
further
applications.
In
this
work,
based
on
unique
coordination
mode
pincer
ligand-stabilized
nanocluster
Au8(PNP)4,
we
revealed
site-recognition
mechanism
for
transformations
nanoclusters.
"open
nitrogen
sites"
surface
interact
with
different
inducers
including
organic
compounds
metals
trigger
conversion
Au8(PNP)4
Au13
Au9Ag4
respectively.
Control
experiments
verified
mechanism,
femtosecond
nanosecond
transient
absorption
spectroscopy
electronic
photoluminescent
evolution
accompanied
by
transformation.
Chemistry - A European Journal,
Journal Year:
2024,
Volume and Issue:
30(28)
Published: March 12, 2024
Owing
to
distinct
physicochemical
properties
in
comparison
gold
and
silver
counterparts,
atomically
precise
copper
nanoclusters
are
attracting
embryonic
interest
material
science.
The
introduction
of
cluster
nanomaterials
more
interesting
fields
is
currently
urgent
desired.
Reported
this
work
novel
[XCu
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(18), P. 12734 - 12742
Published: April 9, 2024
Innovative
surface-protecting
ligands
are
in
constant
demand
due
to
their
crucial
role
shaping
the
configuration,
property,
and
application
of
gold
nanoclusters.
Here,
unprecedented
O-ethyl
dithiocarbonate
(DTX)-stabilized
atomically
precise
nanoclusters,
[Au25(PPh3)10(DTX)5Cl2]2+
(Au25DTX-Cl)
[Au25(PPh3)10(DTX)5Br2]2+
(Au25DTX-Br),
were
synthesized
structurally
characterized.
The
introduction
bidentate
DTX
not
only
endowed
nanocluster
with
unique
staggered
Au25
nanorod
configurations
but
also
generated
symmetry
breaking
from
D5d
geometry
kernels
chiral
D5
configuration
molecules.
chirality
nanorods
was
notably
revealed
through
single-crystal
X-ray
diffraction,
separation
induced
by
employing
ligands.
nanorods,
as
opposed
eclipsed
ones,
responsible
for
large
red
shift
emission
wavelengths,
giving
rise
a
promising
near-infrared
II
(NIR-II,
>1000
nm)
phosphorescence.
Furthermore,
performances
photocatalytic
sulfide
oxidation
electrocatalytic
hydrogen
evolution
reactions
have
been
examined,
it
has
demonstrated
that
outstanding
catalytic
activity
nanoclusters
is
highly
related
stability.
Small,
Journal Year:
2024,
Volume and Issue:
20(32)
Published: March 22, 2024
Abstract
Atomically
precise
metal
clusters
serve
as
a
unique
model
for
unraveling
the
intricate
mechanism
of
catalytic
reaction
and
exploring
complex
relationship
between
structure
activity.
Herein,
three
series
water‐soluble
heterometallic
LnCu
6
,
abbreviated
‐AC
(Ln
=
La,
Nd,
Gd,
Er,
Yb;
HAC
acetic
acid),
‐IM
La
Nd;
IM
Imidazole),
‐IDA
H
2
IDA
Iminodiacetic
acid)
are
presented,
each
featuring
uniform
metallic
core
stabilized
by
distinct
protected
ligands.
Crystal
analysis
reveals
triangular
prism
topology
formed
six
Cu
2+
ions
around
one
Ln
3+
ion
in
with
variations
Cu···Cu
distances
attributed
to
different
Electrocatalytic
oxygen
evolution
(OER)
shows
that
these
exhibit
OER
activities
remarkable
turnover
frequency
135
s
−1
NdCu
79
32
.
Structural
Density
Functional
Theory
(DFT)
calculations
underscore
correlation
shorter
improves
activity,
emphasizing
pivotal
role
active‐site
distance
regulating
electrocatalytic
activities.
These
results
provide
valuable
insights
into
contribute
design
efficient
homogeneous
electrocatalysts.
Nano Letters,
Journal Year:
2023,
Volume and Issue:
23(16), P. 7508 - 7515
Published: July 21, 2023
Practical
approaches
to
the
synthesis
of
atomically
precise
metal
nanoclusters
are
in
high
demand
as
they
provide
structural
basis
for
investigating
nanomaterials'
structure-property
correlations
with
atomic
precision.
The
Brust-Schiffrin
method
has
been
widely
used,
while
essential
reductive
ligands
(e.g.,
thiols)
limit
application
this
synthesizing
specific
frameworks
and
surface
ligands.
In
work,
we
developed
a
photochemical
route
by
applying
disulfide,
which
is
available,
stable,
environmentally
friendly
sulfur
source.
This
enables
construction
structurally
diverse
especially
features
PhS-protected
that
were
not
easily
achieved
previously
gram-scale
synthesis.
A
reduction-oxidation
cascade
mechanism
revealed
route.
work
expected
open
up
new
opportunities
nanocluster
will
contribute
practical
applications
kind
nanomaterial.
Small,
Journal Year:
2024,
Volume and Issue:
20(29)
Published: Feb. 22, 2024
The
performance
of
Stimulated
Emission
Depletion
(STED)
microscopy
depends
critically
on
the
fluorescent
probe.
Ultrasmall
Au
nanoclusters
(Au
NCs)
exhibit
large
Stokes
shift,
and
good
stimulated
emission
response,
which
are
potentially
useful
for
STED
imaging.
However,
NCs
polydispersed
in
size,
sensitive
to
surrounding
environment,
difficult
control
surface
functional
group
stoichiometry,
results
reduced
density
high
heterogeneity
labeling
biological
structures.
Here,
this
limitation
is
overcome
by
developing
a
method
encapsulate
ultrasmall
with
DNA
cages,
yielded
monodispersed,
monofunctionalized
that
long-term
stable.
Moreover,
DNA-caging
also
greatly
improved
fluorescence
quantum
yield
photostability
NCs.
In
imaging,
DNA-caged
≈40
nm
spatial
resolution
able
resolve
microtubule
line
shapes
homogeneity.
contrast,
without
caging,
NCs-DNA
conjugates
only
achieved
≈55
spotted,
poorly
resolved
structures,
due
presence
aggregates.
Overall,
developed
achieve
precise
functionalization
improve
monodispersity,
stability,
as
well
optical
properties
NCs,
providing
promising
class
probes
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(29)
Published: May 7, 2024
A
gold(I)-cluster-based
twin-cage
has
been
constructed
by
post-clustering
covalent
modification
of
a
hexa-aldehyde
cluster
precursor
with
triaminotriethylamines.
The
cages-on-cluster
structure
double
cavities
and
four
binding
sites,
which
show
site-discriminative
for
silver(I)
copper(I)
guests.
guests
in
the
tripodal
hats
affect
luminescence
cluster:
tetra-silver(I)
host-guest
complex
is
weakly
red-emissive,
while
bis-copper(I)-bis-silver(I)
one
non-emissive
but
stimuli-responsive
supramolecule.
ion
inside
tri-imine
cavity
oxidation
sensitive,
enables
release
bright
emissive
triggered
H
