Site-specific substitution in atomically precise carboranethiol-protected nanoclusters and concomitant changes in electronic properties
Vivek Yadav,
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Arijit Jana,
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Swetashree Acharya
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et al.
Nature Communications,
Journal Year:
2025,
Volume and Issue:
16(1)
Published: Jan. 30, 2025
We
report
the
synthesis
of
[Ag17(o1-CBT)12]3-
abbreviated
as
Ag17,
a
stable
8e⁻
anionic
cluster
with
unique
Ag@Ag12@Ag4
core-shell
structure,
where
o1-CBT
is
ortho-carborane-1-thiol.
By
substituting
Ag
atoms
Au
and/or
Cu
at
specific
sites
we
created
isostructural
clusters
[AuAg16(o1-CBT)12]3-
(AuAg16),
[Ag13Cu4(o1-CBT)12]3-
(Ag13Cu4)
and
[AuAg12Cu4(o1-CBT)12]3-
(AuAg12Cu4).
These
substitutions
make
systematic
modulation
their
structural
electronic
properties.
show
that
preferentially
occupies
core,
while
localizes
in
tetrahedral
shell,
influencing
stability
diversity
clusters.
The
band
gap
expands
systematically
(2.09
eV
for
Ag17
to
2.28
AuAg12Cu4),
altering
optical
absorption
emission.
Ultrafast
measurements
reveal
longer
excited-state
lifetimes
Cu-containing
clusters,
highlighting
effect
heteroatom
incorporation.
results
demonstrate
tunable
platform
designing
nanoclusters
tailored
properties,
implications
optoelectronics
catalysis.
Tuning
structure
composition
atomically
precise
metal
leads
property
changes
which,
however,
are
still
poorly
understood.
Here,
authors
synthesize
precisely
substituted
analogues
study
luminescence
Language: Английский
Carborane Meets Metal Nanocluster: New Opportunities in Nanomaterials
Jia‐Hong Huang,
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Yao Cui,
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Zhaoyang Wang
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et al.
Accounts of Chemical Research,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 28, 2025
ConspectusMetal
nanoclusters,
distinguished
by
their
atom-precise
structures
and
quantum
size
effect,
are
regarded
as
a
crucial
bridge
between
organometallic
complexes
plasmonic
metal
nanoparticles.
These
nanoclusters
primarily
composed
of
metallic
core
enveloped
protective
ligands,
wherein
the
ligands
play
vital
role
in
determining
nanoclusters'
synthesis,
structural
integrity,
physicochemical
properties.
Considerable
efforts
ligand
engineering
have
concentrated
on
exploring
novel
coordinating
functional
groups
to
advance
nanocluster
research,
particularly
precise
controlled
synthesis
superatomic
fine-tuning
intrinsic
properties,
subsequent
assembly
application.
However,
backbone
these
seems
equally
important
but
attracts
less
attention.
It
is
reasonable
that
if
utility
two
moieties
(coordinating
group
backbone)
provokes
profound
synergistic
contributions
properties
resultant
extremely
inestimable.
In
this
context,
carborane,
with
its
spherical
shape
three-dimensional
aromaticity
(electronic
effect),
has
emerged
promising
candidate
for
design.
Over
past
decades,
incorporation
carborane
into
enabled
construction
various
exhibiting
distinct
architectures,
enhanced
stability,
unique
reactivity.
Therefore,
it
present
current
status
challenges
associated
carboranyl
ligand-protected
guide
future
development.
This
Account
provides
comprehensive
summary
recent
advances
ligand-stabilized
primary
focus
from
our
laboratory.
We
begin
discussing
advantages
introducing
carborane-based
preparation,
particular
emphasis
virtues
heterometal-doped
isostructural
nanoclusters.
Subsequently,
we
summarize
strategies
modification
hierarchical
elucidating
how
facilitates
modulation
specific
promotes
supramolecular
covalent
assembly.
Furthermore,
discuss
cooperativity
achieved
framework
broaden
scope
applications
versatile
fields,
including
hypergolic
fuels,
previously
unexplored
area.
Finally,
facing
research
nido-carborane
or
metallocarborane,
fundamental
understanding
structure–property
relationships,
potential
such
boron
neutron
capture
therapy
radionuclide
extraction.
aims
stimulate
interest
attributes
corresponding
among
students
researchers
across
diverse
disciplines,
chemistry,
crystal
engineering,
materials
science.
Language: Английский
Boosting 2000‐Fold Hypergolic Ignition Rate of Carborane by Substitutes Migration in Metal Clusters
Jia‐Hong Huang,
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Ao‐Qi Ji,
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Zhaoyang Wang
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et al.
Advanced Science,
Journal Year:
2024,
Volume and Issue:
11(23)
Published: April 3, 2024
Abstract
Hypergolic
propellants
rely
on
fuel
and
oxidizer
that
spontaneously
ignite
upon
contact,
which
fulfill
a
wide
variety
of
mission
roles
in
launch
vehicles
spacecraft.
Energy‐rich
carboranes
are
promising
hypergolic
fuels,
but
triggering
their
energy
release
is
quite
difficult
because
ultrastable
aromatic
cage
structure.
To
steer
the
development
carborane‐based
high‐performance
material,
carboranylthiolated
compounds
integrated
with
atomically
precise
copper
clusters
presented,
yielding
two
distinct
isomers,
Cu
14B‐S
14C‐S
,
both
possessing
similar
ligands
core
structures.
With
migration
thiolate
groups
from
carbon
atoms
to
boron
atoms,
ignition
delay
(ID)
time
shortened
6870
3
ms
when
contacted
environmentally
benign
high‐test
peroxide
(HTP,
H
2
O
concentration
90%).
The
extraordinarily
short
ID
ranking
among
best
HTP‐active
materials.
experimental
theoretical
findings
reveal
benefitting
groups,
characterized
by
an
electron‐rich
metal
kernel,
displays
enhanced
reducibility
superior
charge
transfer
efficiency.
This
results
exceptional
activation
rates
HTP,
consequently
inducing
carborane
combustion
simultaneous
energy.
fundamental
investigation
shed
light
advanced
green
propulsion
systems.
Language: Английский
Structure‐Induced Energetic Coordination Compounds as Additives for Laser Initiation Primary Explosives
Meng Cui,
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Yun‐Fan Yan,
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Rui‐Xuan Qian
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et al.
Advanced Materials,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Dec. 9, 2024
Laser
ignition
of
primary
explosives
presents
more
reliable
alternative
to
traditional
electrical
initiation
methods.
However,
the
commercial
initiator
lead
azide
(LA)
requires
a
high-power
density
laser
detonate,
with
minimum
energy
(E
Language: Английский
High-Performance Hypergolic Fuels Based on Copper Hydride Clusters
Chao Wang,
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Run-Meng Li,
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Zheng Duan
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et al.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: May 16, 2025
The
development
of
novel
high-performance
hypergolic
fuels
is
crucial
for
the
advancement
aerospace
industry.
Although
hydride-containing
compounds
offer
excellent
combustion
properties
and
a
short
ignition
delay
time,
their
inherent
instability
strong
reducing
nature
have
hindered
widespread
application.
Herein,
we
report
synthesis
characterization
an
energetic,
atomically
precise
copper
hydride
cluster,
Cu11H3(5N-dpf)6(OAc)2,
denoted
as
Cu11H3.
This
cluster
exhibits
exceptional
performance
good
stability.
When
paired
with
high-test
peroxide
(HTP,
>90%
H2O2),
Cu11H3
demonstrates
time
16
ms
achieves
high
specific
impulse
254
s.
Both
experimental
theoretical
studies
suggest
that
hydrides
play
pivotal
role
in
process
through
interactions
protons
from
H2O2,
leading
to
hydrogen
evolution
accelerated
combustion.
research
provides
valuable
insights
design
novel,
environmentally
benign
solid
propulsion
applications.
Language: Английский
Structural anchoring of highly reactive CBH− for high-performance hypergolic coordination polymers with excellent thermal stability
Qin Wang,
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Meng Cui,
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Pei‐Kuen Wei
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et al.
Inorganic Chemistry Frontiers,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 1, 2025
The
synthesis
of
energetic
BH
3
CN
−
anion
polymers
within
the
structure
for
propellant
fuels
aims
to
achieve
high
energy
density,
ultra-fast
response,
and
unparalleled
thermal
stability
in
hypergolic
materials.
Language: Английский