The Journal of Physical Chemistry C,
Год журнала:
2024,
Номер
128(31), С. 13264 - 13270
Опубликована: Июль 25, 2024
In
the
present
work,
two
viologen
derivatives
were
synthesized
and
used
in
molecular
junctions
(MJs)
to
investigate
impact
of
a
decoupling
unit
on
rectification
behavior.
Both
bear
an
aniline
terminal
but
one
derivative
(named
VIO-C1)
is
terminated
by
methyl
group
whereas
other
VIO-C6)
bears
six-carbon
(C6H13)
chain.
Thin
layers
each
deposited
gold
microelectrodes
electroreduction
corresponding
diazonium
reagents,
solid-state
MJs
fabricated
study
electronic
transport.
JV
curves
VIO-C1
show
symmetric
behavior,
VIO-C6
(with
alkyl
chain)
strong
asymmetry
This
behavior
attributed
decrease
coupling
at
top
interface
due
chain
confirmed
comparison
with
similar
which
thin
AlOx
layer
inserted
layer.
The
this
ratio
discussed.
Stable
radicals
are
spin-active
species
with
a
plethora
of
proposed
applications
in
fields
from
energy
storage
and
molecular
electronics
to
quantum
communications.
However,
their
optical
properties
vibrational
modes
so
far
not
well
understood.
Furthermore,
it
is
yet
clear
how
these
affected
by
the
radical
oxidation
state,
which
key
understanding
electronic
transport.
Here,
we
identify
1,2,4-benzotriazin-4-yl,
stable
doubly
thiolated
variant
Blatter
radical,
using
surface-enhanced
Raman
scattering
(SERS).
Embedding
monolayers
plasmonic
nanocavities
gives
access
modes,
photoluminescence,
response
during
redox
processes.
We
reveal
influence
adjacent
metallic
surfaces
fluctuating
SERS
signals
that
suggest
coupling
between
unpaired
electron
spatially
overlapping
mode.
This
can
potentially
be
exploited
for
information-storage
devices
chemically
designed
qubits.
Noncovalent
interactions,
both
between
molecules
and
at
the
molecule–electrode
interfaces,
play
essential
roles
in
enabling
dynamic
reversible
molecular
behaviors,
including
self-assembly,
recognition,
various
functional
properties.
In
macroscopic
ensemble
systems,
these
interfacial
phenomena
often
exhibit
emergent
properties
that
arise
from
synergistic
interplay
of
multiple
noncovalent
interactions.
However,
single-molecule
scale,
precisely
distinguishing,
characterizing,
controlling
individual
interactions
remains
a
significant
challenge.
Molecular
electronics
offers
unique
platform
for
constructing
characterizing
intermolecular
interfaces
governed
by
isolated
study
fundamental
Furthermore,
precise
control
over
through
facilitates
development
enhanced
devices.
This
review
examines
characterization
arising
electrical
measurements
explores
their
applications
We
begin
discussing
construction
stable
junctions
followed
an
analysis
electron
tunneling
mechanisms
mediated
key
modulation
methods.
then
investigate
how
enhance
device
sensitivity,
stability,
functionality,
establishing
design
principles
next-generation
electronics.
have
also
explored
potential
bottom-up
self-assembled
The
concludes
addressing
opportunities
challenges
scaling
up
Abstract
Coordination‐driven
supramolecular
assemblies
are
promising
for
nanometer‐sized
electronic
devices
due
to
the
potential
manipulate
metal–ligand
interactions
and
thereby
control
charge
transport
via
tunneling
through
these
assemblies.
Cross‐plane
is
investigated
in
of
metalloporphyrins
pillar
molecules,
specifically
palladium(II)
zinc(II)
octaethylporphyrin
(PdOEP
ZnOEP)
monolayers
bilayers
with
bidentate
(DABCO)
monodentate
(ABCO)
ligands
on
highly
oriented
pyrolytic
graphite
(HOPG).
Junction
measurements
quantum‐chemical
calculations
reveal
that
significantly
influence
thermoelectric
effects.
Weak
PdOEP
create
isolated
molecular
orbitals
interior
ligands,
compressing
HOMO‐LUMO
gap
enhancing
currents
unusual,
inverted
attenuation
behavior
high
thermopower.
Conversely,
strong
ZnOEP
induce
localized
porphyrin,
leading
conventional
decay
low
The
study
highlights
as
a
strategy
engineer
orbital
distribution,
quantum
efficiency
molecular‐scale
devices.
ABSTRACT
Molecular
electronics
has
emerged
and
evolved
within
the
context
of
miniaturization
silicon‐based
microchips,
with
purpose
to
achieve
conducting
functions
by
integrating
individual
molecules
into
circuits
through
a
“bottom‐up”
approach,
but
exploration
intrinsic
physical
phenomena
operational
principles
is
still
in
infancy
stage.
One
biggest
challenges
arises
from
fundamental
difference
charge
transport
modes
between
conventional
macroscopic
molecular
microscopic
circuits.
The
former
follows
Ohm's
law,
while
latter
operates
via
quantum
transport.
Undoubtedly,
deep
understanding
mechanisms
governing
complex
essential
for
moving
molecular‐scale
devices
laboratory
large‐scale
production.
Here,
we
review
fields
topology
perspective
propose
straightforward
definition
differentiate
single‐channel
multi‐channel
We
detail
previously
reported
models
analyze
their
structure–property
relationships.
also
compare
conductance
multiple
channels
those
single
channels,
giving
special
attention
impact
noncovalent
such
as
through‐space
conjugation.
Lastly,
discuss
opportunities
single‐molecule
systems
highlighting
advantages
envisioning
potential
applications.
Chemical Science,
Год журнала:
2024,
Номер
15(25), С. 9510 - 9556
Опубликована: Янв. 1, 2024
This
article
provides
an
overview
of
measurement
methods
and
interpretations
data
in
the
field
molecular
electronics,
together
with
a
summary
predictive
models
that
assist
establishing
robust
structure–property
relationships.
Angewandte Chemie,
Год журнала:
2024,
Номер
136(23)
Опубликована: Апрель 5, 2024
Abstract
The
intrinsic
activity
assessment
of
transition
metal
oxides
(TMOs)
as
key
electrocatalysts
for
the
oxygen
evolution
reaction
(OER)
has
not
been
standardized
due
to
uncertainties
regarding
their
structure
and
composition,
difficulties
in
accurately
measuring
electrochemically
active
surface
area
(ECSA),
deficiencies
mass‐transfer
(MT)
rates
conventional
measurements.
To
address
these
issues,
we
utilized
an
electrodeposition‐thermal
annealing
method
precisely
synthesize
single‐particle
TMOs
with
well‐defined
composition.
Concurrently,
engineered
low
roughness,
spherical
surfaces
individual
particles,
enabling
precise
measurement
ECSA.
Furthermore,
by
constructing
a
conductor‐core
semiconductor‐shell
structure,
evaluated
inherent
OER
perovskite‐type
semiconductor
materials,
broadening
scope
beyond
just
conductive
TMOs.
Finally,
using
nanoelectrode
technique,
systematically
measured
TMO
particles
various
sizes
OER,
overcoming
MT
limitations
seen
approaches.
These
improvements
have
led
us
propose
reliable
approach
evaluating
TMOs,
only
validating
accuracy
theoretical
calculations
but
also
revealing
strong
correlation
on
melting
point
This
discovery
holds
significant
importance
future
high‐throughput
material
research
applications,
offering
valuable
insights
electrocatalysis.
The Journal of Physical Chemistry C,
Год журнала:
2024,
Номер
128(31), С. 13264 - 13270
Опубликована: Июль 25, 2024
In
the
present
work,
two
viologen
derivatives
were
synthesized
and
used
in
molecular
junctions
(MJs)
to
investigate
impact
of
a
decoupling
unit
on
rectification
behavior.
Both
bear
an
aniline
terminal
but
one
derivative
(named
VIO-C1)
is
terminated
by
methyl
group
whereas
other
VIO-C6)
bears
six-carbon
(C6H13)
chain.
Thin
layers
each
deposited
gold
microelectrodes
electroreduction
corresponding
diazonium
reagents,
solid-state
MJs
fabricated
study
electronic
transport.
JV
curves
VIO-C1
show
symmetric
behavior,
VIO-C6
(with
alkyl
chain)
strong
asymmetry
This
behavior
attributed
decrease
coupling
at
top
interface
due
chain
confirmed
comparison
with
similar
which
thin
AlOx
layer
inserted
layer.
The
this
ratio
discussed.
