Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(5), С. 3331 - 3342
Опубликована: Янв. 29, 2024
The
isolation
of
formally
two-coordinate
lanthanide
(Ln)
complexes
is
synthetically
challenging,
due
to
predominantly
ionic
Ln
bonding
regimes
favoring
high
coordination
numbers.
In
2015,
it
was
predicted
that
a
near-linear
dysprosium
bis(amide)
cation
[Dy{N(Si
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(28), С. 18899 - 18904
Опубликована: Июль 8, 2024
In
recent
years,
dysprosium
macrocycle
single-molecule
magnets
(SMMs)
have
received
increasing
attention
due
to
their
excellent
air/thermal
stability,
strong
magnetic
anisotropy,
and
rigid
molecular
skeleton.
However,
they
usually
display
fast
zero-field
quantum
tunneling
of
the
magnetization
(QTM)
rate,
severely
hindering
data
storage
applications.
Herein,
we
report
design,
synthesis,
characterization
an
air-stable
monodecker
didysprosium
integrating
single-ion
near-perfect
local
crystal
field
(CF)
symmetry,
efficient
exchange
bias.
These
indispensable
features
enable
clear-cut
elucidation
crucial
role
very
weak
antiferromagnetic
coupling
on
dynamics,
creating
a
prominent
SMM
with
large
effective
energy
barrier
(
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Янв. 12, 2024
Abstract
Single-molecule
magnets
are
among
the
most
promising
platforms
for
achieving
molecular-scale
data
storage
and
processing.
Their
magnetisation
dynamics
determined
by
interplay
between
electronic
vibrational
degrees
of
freedom,
which
can
couple
coherently,
leading
to
complex
vibronic
dynamics.
Building
on
an
ab
initio
description
Hamiltonians,
we
formulate
a
non-perturbative
model
low-energy
magnetic
freedom
in
monometallic
single-molecule
magnets.
Describing
their
low-temperature
magnetism
terms
polarons,
able
quantify
contribution
quantum
tunnelling
magnetisation,
process
that
is
commonly
assumed
be
independent
spin-phonon
coupling.
We
find
formation
polarons
lowers
probability
both
amorphous
crystalline
systems
stabilising
low-lying
spin
states.
This
work,
thus,
shows
coupling
subtly
influences
relaxation
even
at
extremely
low
temperatures
where
no
excitations
present.
The Journal of Physical Chemistry C,
Год журнала:
2024,
Номер
128(12), С. 4882 - 4890
Опубликована: Март 15, 2024
Single
molecule
magnets
(SMMs)
constitute
a
pivotal
class
of
nanoscale
molecular
with
promising
potential
across
various
domains
such
as
high-density
information
storage,
quantum
computing,
and
spin
electron
devices.
Among
these,
lanthanide-based
SMMs
have
garnered
significant
attention
in
recent
research
due
to
their
distinctive
magnetic
coordination
properties,
offering
prospects
for
substantial
advancements
storage
technologies.
Over
the
past
three
decades,
considerable
efforts
been
directed
toward
developing
novel
characterized
by
anisotropy
barrier
blocking
temperature,
leading
strides
field.
This
perspective
delves
into
latest
developments
structure
performance
lanthanide
SMMs,
providing
valuable
insights
optimizing
functionality.
The
roles
ligands
central
atoms
modulating
are
emphasized
alongside
strategies
augment
explore
surface
applications.
Additionally,
this
explores
fusion
theoretical
machine
learning
methodologies
identify
highly
anisotropic
thereby
outlining
roadmap
functionality
SMMs.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(38)
Опубликована: Июль 2, 2024
Lanthanide
(Ln)
based
mononuclear
single-molecule
magnets
(SMMs)
provide
probably
the
finest
ligand
regulation
model
for
magnetic
property.
Recently,
development
of
such
SMMs
has
witnessed
a
fast
transition
from
coordination
to
organometallic
complexes
because
latter
provides
fertile,
yet
not
fully
excavated
soil
SMMs.
Especially
those
with
heterocyclic
ligands
have
shown
potential
reach
higher
blocking
temperature.
In
this
minireview,
we
give
an
overview
design
principle
and
highlight
"shining
stars"
organolanthanide
on
ring
sizes
ligands,
analysing
how
electronic
structures
stiffness
subsequently
formed
molecules
affect
dynamic
magnetism
Finally,
envisaged
future
Ln-SMMs.
Nature Communications,
Год журнала:
2025,
Номер
16(1)
Опубликована: Март 4, 2025
Metal-organic
compounds
that
feature
magnetic
bistability
have
been
proposed
as
bits
for
storage,
but
progress
has
slow.
Four-coordinate
cobalt(II)
complexes
high
inversion
barriers
of
the
moment,
they
lack
bistability.
Developing
radical-bridged
polynuclear
systems
is
a
promising
strategy
to
encounter
this;
however
detailed
investigations
such
species
are
scarce.
We
report
an
air-stable
dinuclear
complex,
studied
by
combination
magnetometry
and
spectroscopy.
Fits
data
give
D
=
-113
cm-1
zero-field
splitting
(ZFS)
J
390
metal-radical
exchange.
Ab
initio
reveal
first-order
spin-orbit
coupling
quasi-degenerate
dx2-y2
dxy
orbitals
be
at
heart
large
ZFS.
The
corresponding
transitions
spectroscopically
observed,
related
exchange
coupling.
Finally,
signatures
spin-phonon
observed
theoretically
analyzed.
Furthermore,
we
demonstrate
spectral
features
not
predominantly
spin
excitations,
largely
vibrational
in
character.
European Journal of Inorganic Chemistry,
Год журнала:
2023,
Номер
26(35)
Опубликована: Июль 7, 2023
Abstract
The
number
of
scientific
articles
that
need
to
be
considered
cover
a
research
topic
is
ever‐increasing
and
quite
difficult
for
newcomer
assimilate.
This
particularly
true
in
dynamic
discipline
like
Molecular
Magnetism.
In
order
help
young
researchers
this
field,
article
proposes
“review
reviews”
also
known
as
an
“umbrella
review”
on
lanthanide‐based
single‐molecule
magnets
(
4
f
‐SMM).
As
preamble,
various
bibliographic
search
techniques
AI‐based
tools
search,
indexing,
summarization
are
proposed
commented.
Then,
the
main
milestones
‐SMM
identified.
core
paper,
books,
book
articles,
reviews
dealing
with
contextualized
classified
by
subtopics.
therefore
gateway
field.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(40), С. 22265 - 22275
Опубликована: Сен. 29, 2023
We
present
a
wide-ranging
interrogation
of
the
border
between
single-molecule
and
solid-state
magnetism
through
study
erbium-based
Ising-type
magnetic
compounds
with
fixed
unit,
using
three
different
charge-balancing
cations
as
means
to
modulate
crystal
packing
environment.
Properties
rooted
in
isolated
spin
Hamiltonian
remain
fixed,
yet
careful
observation
dynamics
reveals
breakdown
this
approximation
number
interesting
ways.
First,
differences
lead
striking
3
orders
magnitude
suppression
relaxation
rates,
indicating
rich
interplay
intermolecular
interactions
governed
by
anisotropic
Ising
lattice
stabilization
localized
slow
driven
spin-forbidden
nature
quantum
tunneling
f-electron-based
magnetization.
By
diverse
rigorous
physical
methods,
including
temperature-dependent
X-ray
crystallography,
field,
temperature,
time-dependent
magnetometry,
application
new
magnetization
fitting
technique
quantify
susceptibility
peakshape,
we
are
able
construct
more
nuanced
view
role
nonzero-dimensional
can
play
what
predominantly
considered
zero-dimensional
materials.
Specifically,
use
low
field
virgin-curve
analysis
isolate
metamagnetic
spin-flip
transitions
each
system
strength
corresponding
expected
internal
dipole-dipole
lattice.
This
behavior
is
vital
complete
interpretation
likely
common
for
systems
such
high
anisotropy.
collective
interactivity
opens
realm
possibility
molecular
materials,
where
their
unprecedented
anisotropy
determining
factor
building
higher
dimensionality.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
unknown
Опубликована: Ноя. 2, 2023
Molecular
materials
are
poised
to
play
a
significant
role
in
the
development
of
future
optoelectronic
and
quantum
technologies.
A
crucial
aspect
these
areas
is
spin-phonon
coupling
how
it
facilitates
energy
transfer
processes
such
as
intersystem
crossing,
decoherence,
magnetic
relaxation.
Thus,
interest
be
able
accurately
calculate
molecular
spin
dynamics
condensed
phase.
Here,
we
demonstrate
maturity
ab
initio
methods
for
calculating
by
performing
case
study
on
single-molecule
magnet
showing
quantitative
agreement
with
experiment,
allowing
us
explore
underlying
origins
its
dynamics.
This
feat
achieved
leveraging
our
recent
developments
analytic
calculations
conjunction
new
method
including
infinite
electrostatic
potential
calculations.
Furthermore,
make
first
determination
phonon
lifetimes
line
widths
prove
that
commonplace
Born-Markov
assumption
valid,
but
"exact"
not
essential
obtain
accurate
relaxation
rates.
Calculations
using
this
approach
facilitated
open-source
packages
have
developed,
enabling
cost-effective
solids.
The Journal of Physical Chemistry Letters,
Год журнала:
2023,
Номер
14(34), С. 7658 - 7664
Опубликована: Авг. 21, 2023
Paramagnetic
molecules
offer
unique
advantages
for
quantum
information
science
owing
to
their
spatial
compactness,
synthetic
tunability,
room-temperature
coherence,
and
potential
optical
state
initialization
readout.
However,
current
optically
addressable
molecular
qubits
are
hampered
by
rapid
spin-lattice
relaxation
(T1)
even
at
sub-liquid
nitrogen
temperatures.
Here,
we
use
temperature-
orientation-dependent
pulsed
electron
paramagnetic
resonance
(EPR)
elucidate
the
negative
sign
of
ground
zero-field
splitting
(ZFS)
assign
T1
anisotropy
specific
types
motion
in
an
S
=
1
Cr(o-tolyl)4
qubit.
The
displays
a
distinct
sin2(2θ)
functional
form
that
is
not
observed
1/2
Cu(acac)2
or
other
Cu(II)/V(IV)
microwave
qubits.
Cr(o-tolyl)4T1
ascribed
couplings
between
spins
rotational
low-energy
acoustic
pseudoacoustic
phonons.
Our
findings
suggest
degrees
freedom
should
be
suppressed
maximize
coherence
temperature
