Inorganic Chemistry,
Год журнала:
2024,
Номер
64(1), С. 701 - 715
Опубликована: Дек. 21, 2024
The
dinuclear
β-diketiminato
complex
[L1ClDy(μ-Cl)3DyL1(THF)]
(1)
(L1
=
{2,6-iPr2C6H3–NC(Me)CHC(Me)N-2,6-iPr2C6H3}−)
was
obtained
by
reaction
of
DyCl3
with
KL1
in
a
molar
ratio
1:1
and
used
for
the
preparation
mixed-ligand
[L1Dy(μ-3,5-Cat)]2
(2)
salt
metathesis
3,5-CatK2
(3,5-Cat
−3,5-di-tert-butyl-catecholate).
Reactions
3,5-CatNa2
[L2LnCl2(THF)2]
(Ln3+
Dy,
Y)
ligated
less
bulky
ligand
L2
{2,4,6-Me3C6H2–NC(Me)CHC(Me)N-2,4,6-Me3C6H2}−
afforded
THF-containing
complexes
[L2Ln(μ-3,5-Cat)(THF)]2
Dy
(3a),
Y
(3b)).
All
new
were
fully
characterized,
solid-state
structures
determined
single-crystal
X-ray
diffraction.
Magnetic
measurements
revealed
single-molecule
magnet
behavior
dysprosium
complexes.
Sub-Kelvin
μSQUID
studies
confirm
SMM
character
systems,
while
CASSCF
calculation
along
simulation
experimental
data
yields
an
antiferromagnetic
interaction
operating
between
Dy3+
ions.
Molecules,
Год журнала:
2024,
Номер
29(3), С. 688 - 688
Опубликована: Фев. 1, 2024
Rare
earths,
scandium,
yttrium,
and
the
fifteen
lanthanoids
from
lanthanum
to
lutetium,
are
classified
as
critical
metals
because
of
their
ubiquity
in
daily
life.
They
present
magnets
cars,
especially
electric
cars;
green
electricity
generating
systems
computers;
steel
manufacturing;
glass
light
emission
materials
for
safety
lighting
lasers;
exhaust
catalysts
supports;
artificial
rubber
production;
agriculture
animal
husbandry;
health
cancer
diagnosis
treatment;
a
variety
electronic
products
essential
modern
living.
have
potential
replace
toxic
chromates
corrosion
inhibition,
magnetic
refrigeration,
new
materials,
role
may
expand.
This
review
examines
sustainability,
environment,
recycling,
crop
production,
feedstocks,
catalysis,
health,
well
considering
future
uses.
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.
Inorganic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 14, 2025
Understanding
the
ligand
field
interactions
in
lanthanide-containing
magnetic
molecular
complexes
is
of
paramount
importance
for
understanding
their
properties,
and
simple
models
rationalizing
effects
are
much
desired.
In
this
work,
equivalence
between
electrostatic
models,
which
derive
results
from
calculating
interaction
energy
charge
density
4f
electrons
an
potential
representing
ligands,
common
quantum
mechanical
effective
spin
Hamiltonian
space
ground
J
multiplet
formulated
detail.
This
enables
construction
any
given
discusses
terms
a
generalized
with
potential.
Such
often
allow
easier
rationalization
interactions,
it
can
be
hoped
that
work
will
help
us
to
better
understand
lanthanide
complexes.
Russian Journal of Coordination Chemistry,
Год журнала:
2024,
Номер
50(6), С. 363 - 373
Опубликована: Июнь 1, 2024
Abstract
The
measurement
of
the
dynamic
magnetic
susceptibility
is
a
universal
method,
which
used
for
evaluation
properties
single
molecule
magnets
by
scientists
all
over
world.
An
information
in
Russian
scientific
literature
that
can
be
useful
practical
mastering
this
method
presently
insufficient.
To
fill
gap,
work
we
present
detailed
procedure
magnetochemical
experiment
observing
slow
relaxation
coordination
compounds
3
d
-
and
4
f
-element
ions
complete
characterization
dynamics
behavior.
Special
attention
given
to
usually
omitted
but
important
details
related
stages
studying
dynamics.
main
variants
sample
preparation
are
described,
logics
construction
measuring
sequence
experimental
data
processing
discussed,
advantages
drawbacks
some
programs
calculation
considered.
concepts
equations
analysis
presented,
primary
conclusions
made
from
obtained
results
proposed.
Inorganic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 31, 2025
Multimetallic
half-sandwich
complexes
of
the
paramagnetic
lanthanides
gadolinium,
terbium,
dysprosium,
holmium,
and
erbium
as
well
diamagnetic
yttrium
are
readily
accessible
via
AlMe4/halogenido
exchange
reactions
Cp*Ln(AlMe4)2
with
mild
halogenido
transfer
reagents
Me3SiI
Me3GeX
(Cp*
=
C5Me5;
X
Br,
Cl).
Depending
on
rare-earth-metal
center
ion
size,
distinct
structural
motifs
nuclearities
obtained,
including
dimeric
compounds
[Cp*Ln(AlMe4)(μ2-Cl)]2
for
smaller
metal
centers
Ln
Ho,
Er,
iodido-bridged
tetranuclear
rings
[Cp*Ln(μ2-I)2]4
(Ln
Y,
Tb,
Dy,
Er),
a
heterobimetallic
tetramethylaluminato-bridged
gadolinium
cluster
[Cp*4Gd4I7(AlMe4)]2.
The
dysprosium
complex
[Cp*Dy(μ2-I)2]4
shows
single-molecule
magnet
(SMM)
behavior
in
zero
applied
field
an
effective
energy
barrier
164(10)
cm-1.
Inorganic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 17, 2025
Lanthanide-based
single-molecule
magnets
are
attractive
candidates
for
applications
in
quantum
information
processing
or
data
storage.
The
low
symmetry
ligand
field
environment
often
encountered
these
complexes,
combined
with
a
sparsity
of
the
common
magnetic
susceptibility
and
magnetization
recorded
on
powder
samples,
leads
to
massive
overparametrization.
This
limits
application
models,
such
as
point
charge
angular
overlap
describing
data.
In
this
work,
radical
approach
is
taken
consider
models
black
boxes,
whereby
they
suspend
their
chemical
physical
significance.
Instead,
transferability
parameters
across
series
structurally
related
compounds
enforced
achieve
reduced
parametrization.
methodology
applied
four
members
isostructural
[M2IIILn2III(μ3–OH)2(pmide)2(p-Me-PhCO2)6]·2MeCN
(pmideH2
=
N-(2-pyridylmethyl)-iminodiethanol)
butterfly
M
Al,
Fe,
Ln
Er,
Dy.
It
shown
that
can
be
described
simultaneously
remarkable
accuracy
using
only
two
characterizing
lanthanide
fields
all
compounds.
Interestingly,
resulting
parametrization
its
values
lie
within
range
intuition
despite
box
procedure
used
obtain
them.
Implications
discussed.
Inorganic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 10, 2025
The
ligand
field
interactions
in
lanthanide-based
magnetic
molecular
complexes
are
crucial
for
their
properties,
and
simple
models
rationalizing
the
effects
much
desired.
In
this
work,
a
charge-potential
model
is
formulated
detail,
which
describes
as
an
electrostatic
interaction
between
generalized
single-electron
charge
density
representing
4f
electrons
potential
ligands.
equivalent
to
quantum
mechanical
effective
spin
Hamiltonian
space
of
electron
f
orbitals.
Furthermore,
relation
with
many-electron
familiar
ground
J
multiplet
discussed.
This
permits
us
translate
results
any
splittings
multiplet,
includes
high-level
ab
initio
techniques,
into
domain,
vice
versa.
Models
based
on
orbitals
often
well
suited
rationalization,
it
can
be
hoped
that
work
will
help
better
understand
lanthanide
complexes.
Magnetochemistry,
Год журнала:
2025,
Номер
11(4), С. 31 - 31
Опубликована: Апрель 7, 2025
A
ditopic
ligand
(H2L1),
containing
picolinate
subunits
segmented
by
ethynylene
bridges,
has
been
used
in
the
synthesis
of
a
series
isostructural
coordination
polymers,
formulated
as
[(CH3)2NH2][Ln(L1)2]·H2O·CH3COOH,
where
Ln
=
Eu
(1),
Gd
(2),
Tb
(3),
Dy
(4)
and
Ho
(5).
The
single-crystal
structures
show
that
these
compounds
crystallise
orthorhombic
Pna21
space
group
form
3D
anionic
lattices
with
triangular
cavities.
AC
magnetic
susceptibility
measurements
Gd,
derivatives
(2–4)
present
slow
relaxation
their
magnetisation
under
an
applied
DC
field.
detailed
study
2
4
shows
they
relax
following
direct
Orbach
mechanisms
conditions.
derivative
retains
this
behaviour
absence
external
field,
relaxing
via
quantum
tunnelling
mechanisms.
Compound
is
one
very
few
reported
Gd(III)
showing
its
magnetisation.
