ABSTRACT
The
restriction
of
the
molecular
motion
has
been
extensively
exploited
in
tailoring
photoluminescence
(PL)
metal
nanoclusters,
while
activation
such
a
at
level
remains
highly
challenging.
In
this
work,
two‐step
strategy,
that
is,
surface
activating
and
coupling,
was
proposed
to
induce
nanoclusters
level,
corresponding
underwent
emission
appearance
enhancement.
peripheral
phosphine
ligand
functionalization
alkali
cation
introduction
gave
rise
series
structural‐correlated
M
+
‐incorporated
Cu
14
(M
=
Li,
Na,
K,
Rb,
Cs)
with
surface‐aggregation
characteristic,
among
which
K
‐participating
nanocluster
displayed
strongest
fluorescence
intensity
both
solution
crystal
states.
Atomic‐level
structure–property
correlations
were
investigated
rationalize
PL
comparisons.
Overall,
work
offers
new
perspective
for
regulating
via
restricting
their
motions,
hopefully
providing
insight
into
fabrication
emissive
cluster‐based
nanomaterials.
Polyoxometalates,
Год журнала:
2024,
Номер
4(2), С. 9140075 - 9140075
Опубликована: Авг. 7, 2024
As
a
model
system
for
studying
the
structure-and-property
relationship
and
surface
coordination
chemistry
of
metal
nanomaterials,
ligand-stabilized
atomically
precise
coinage-metal
(Au,
Ag,
Cu)
nanoclusters
have
attracted
bolstering
attention.
Considerable
effort
has
been
extended
to
synthesis
structure
determination
in
past
decades,
which
chemical
reduction
high-valence
ions
presence
protective
ligands
lays
foundation.
After
analyzing
over
200
synthetic
examples
individual
prepared
by
direct
method,
with
reactants
either
single
kind
Au,
Cu
or
alloying
(e.g.,
Au-Ag,
Au-Pt),
as
well
phosphines,
thiolates,
alkynyls,
N-heterocyclic
carbenes,
halides
their
combinations,
we
propose
comprehensive
practical
guidelines
nanoclusters.
This
Review
seeks
elucidate
prospective
introduction
robust
prototypes
engineering
nanoclusters,
evolved
from
one-phase,
two-phase,
miscible
solution
solid-state
synthesis.
Several
factors
are
key
optimization,
mainly
including
selection
precursors,
reductant
systems,
purification
strategies.
providing
an
expansive
critical
viewpoint
on
this
rapidly
evolving
field,
some
promising
trends
future
prospected
end.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
64(1)
Опубликована: Сен. 13, 2024
Constructing
structurally
robust
and
catalytically
active
metal
nanoclusters
for
catalyzing
multi-component
reactions
is
an
interesting
while
challenging
task.
Inspired
by
Lewis
acid
base
catalysis,
we
realized
the
combination
of
both
sites
on
surface
a
stable
gold
nanocluster
Au
Advanced Materials,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 13, 2025
Abstract
Precise
doping
is
of
vital
significance
for
atomic
engineering
and
the
establishment
structure‐property
relationships
in
nanocluster
(NC)
chemistry.
Herein,
two
novel
trimetallic
MAu
18
Cd
3
(M
=
Pd/Pt)
NCs
that
are
derived
from
M‐doped
Au
25
templates
24
reported,
which
central
M
atom
surface‐motif
atoms
concurrently
achieved.
Compared
to
original
templates,
Cd‐induced
surface
enhances
rigidity
structural
framework
enlarges
HOMO‐LUMO
gaps
,
significantly
improving
photoluminescent
efficiency
by
suppressing
nonradiative
relaxation.
The
critical
role
(Pd/Pt)
dopant
photoluminescence,
regulates
rate
radiative
decay
excited‐state
electrons,
has
also
been
substantiated.
More
notably,
doped
case
PtAu
exhibits
excellent
photoinitiation
activity
3D
two‐photon
printing
with
a
high
resolution
≈140
nm,
may
be
attributed
prolonged
excited
state.
Overall,
this
work
provides
generalized
routine
precise
synthesis
multi‐metal
concurrent
enhancements
photoluminescence
activity,
expected
stimulate
further
research
design
preparation
multi‐functional,
NCs.
The Journal of Physical Chemistry Letters,
Год журнала:
2025,
Номер
unknown, С. 2942 - 2949
Опубликована: Март 13, 2025
Atomically
precise
metal
nanoclusters
bridge
the
gap
between
atoms
and
nanoparticles,
providing
an
ideal
platform
for
correlating
macroscopic
properties
of
nanoparticles
to
their
microstructures.
In
comparison
rapid
development
coin
nanoclusters,
knowledge
on
group
10
is
relatively
limited
because
active
nature,
resulting
in
synthetic
challenge.
this
work,
we
successfully
synthesize
three
that
is,
Ni3(SNS)3,
Ni3(SNOS)3,
Pd3(SNS)3,
by
using
SNS
pincer
ligands,
which
well-stabilize
nickel
palladium
kernels.
Intrinsic
chirality
originated
from
asymmetric
arrangement
surface
ligands
discovered.
Oxidation-induced
irreversible
transformation
boat-like
Ni3(SNS)3
chair-like
Ni3(SNOS)3
observed,
boat/chair
structure-dependent
reactivity
revealed.
The
structural
features
intriguing
Ni3
Pd3
stabilized
ligand
will
inspire
further
research
nanoclusters.
Chemistry - An Asian Journal,
Год журнала:
2025,
Номер
unknown
Опубликована: Май 29, 2025
Abstract
As
the
new
type
of
molecular
catalysts,
hemilabile
ligand‐protected
Au
nanoclusters
hold
greater
promise
in
realizing
a
better
trade‐off
between
catalytic
activity
and
structural
stability.
Despite
large
amount
(co‐)protected
by
organic
nitrogen
ligands,
little
has
been
known
about
those
containing
dynamically
labile
Au─N
bonds,
where
ligands
are
solely
limited
to
pyridyl‐phosphine.
In
this
study,
we
chose
imidazolyl‐phosphine
(dpim)
as
main
protecting
ligand
synthesized
tetracationic
cluster
[Au
20
6
(dppe)
2
Cl
]
4+
(
‐S
,
dppe
=
Ph
P(CH
)
PPh
),
which
was
structurally
characterized
crystallographically,
spectroscopically,
computationally.
Albeit
similar
electronic
structure
core,
possesses
different
arrangements
positive
charges
from
its
two
reported
analogues,
thus
they
may
serve
an
ideal
triad
for
comparatively
studying
ligand/charge
effect
on
their
activities.
This
work
proved
potential
imidazolyl
phosphine
versatile
syntheses
NCs
with
bonds.
The
imidazolyl‐phosphines
more
amenable
derivatizations,
provides
opportunity
further
enriching
library
potentially
performance.
Deciphering
the
structure-property
relationship
between
cluster
stacking
and
high-efficiency
luminescence
of
metal
nanoclusters
is
crucial
for
designing
synthesizing
high-performance
light-emitting
materials
devices.
Here,
we
successfully
synthesized
two
polymorphic
gold
(Au
8
-C
Au
-P)
investigated
their
stacking-dependent
piezoluminescence
based
on
hydrostatic
pressure.
Under
compression,
exhibits
notable
enhancement.
However,
-P
presents
monotonic
quenching.
High-pressure
structural
characterizations
confirm
existence
anisotropic
compression
in
-P.
high
pressure,
columnar-stacked
shrinks
faster
along
a
axis,
increasing
aspect
ratio
(AR)
fusiform
core.
layered
compressed
c
reducing
AR
leading
to
flatter
femtosecond
transient
absorption,
time-resolved
photoluminescence,
Raman
spectra
collaboratively
that
differentiated
notably
suppresses
nonradiative
loss
caused
by
low-frequency
vibrations
core,
which
responsible
enhancement
-C.
The
emerging
metal
nanoclusters
with
atomically
precise
structures
have
gained
considerable
attention
because
they
exhibit
promising
applications
in
various
fields
and
serve
as
ideal
models
for
studying
the
structure-property
correlation
of
nanoparticles.
Despite
significant
advances,
it
is
still
unclear
how
ligand
diastereomers
impact
stability
chirality
nanoclusters.
In
this
work,
we
systematically
studied
construction
gold
using
PNP
(PNP
=
2,6-bis(1-(diphenylphosphaneyl)ethyl)pyridine)
pincer
consisting
multiple
stereoisomers.
A
metastable
Au6
skeleton
was
found
to
be
a
key
intermediate,
which
can
controlled
aspects
by
selectively
produce
Au9(R,R-PNP)4,
Au9(S,S-PNP)4,
Au9(R,S-PNP)4,
Au6(R,S-PNP)2(R,R-PNP),
Au6(R,S-PNP)2(S,S-PNP)
intriguing
properties
such
self-sorting
spontaneous
resolution.
This
work
provides
strategy
regulating
diastereomers.
