The Journal of Chemical Physics,
Journal Year:
2024,
Volume and Issue:
161(2)
Published: July 10, 2024
Fermi’s
golden
rule
(FGR)
offers
an
empirical
framework
for
understanding
the
dynamics
of
spin–lattice
relaxation
in
magnetic
molecules,
encompassing
mechanisms
like
direct
(one-phonon)
and
Raman
(two-phonon)
processes.
These
principles
effectively
model
experimental
longitudinal
rates,
denoted
as
T1−1.
However,
under
scenarios
increased
coupling
strength
nonlinear
interactions,
FGR’s
applicability
may
diminish.
This
paper
numerically
evaluates
exact
rate
kernels,
employing
extended
dissipaton
equation
motion
formalism.
Our
calculations
reveal
that
when
quadratic
is
considered,
kernels
exhibit
a
free
induction
decay-like
feature,
damping
rates
depend
on
interaction
strength.
We
observe
temperature
dependence
predicted
by
FGR
significantly
deviates
from
results
since
ignores
higher
order
effects
non-Markovian
nature
relaxation.
methods
can
be
easily
to
study
other
systems
with
interactions
provide
valuable
insights
into
T1
molecular
qubits
strong.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(4), P. 2574 - 2582
Published: Jan. 17, 2024
Two-dimensional
conjugated
metal–organic
frameworks
(2D
c-MOFs)
have
attracted
increasing
interest
in
electronics
due
to
their
(semi)conducting
properties.
Charge-neutral
2D
c-MOFs
also
possess
persistent
organic
radicals
that
can
be
viewed
as
spin-concentrated
arrays,
affording
new
opportunities
for
spintronics.
However,
the
strong
π-interaction
between
neighboring
layers
of
layer-stacked
annihilates
active
spin
centers
and
significantly
accelerates
relaxation,
severely
limiting
potential
qubits.
Herein,
we
report
precise
tuning
charge
transport
dynamics
via
control
interlayer
stacking.
The
introduction
bulky
side
groups
on
ligands
enables
a
significant
dislocation
from
serrated
stacking
staggered
stacking,
thereby
spatially
weakening
interactions.
As
consequence,
electrical
conductivity
decreases
by
6
orders
magnitude,
while
density
achieves
more
than
30-fold
increase
spin–lattice
relaxation
time
(T1)
is
increased
up
∼60
μs,
hence
being
superior
reference
with
compact
stackings
whose
too
fast
detected.
Spin
results
reveal
spinless
polaron
pairs
or
bipolarons
play
critical
roles
these
c-MOFs.
Our
strategy
provides
bottom-up
approach
enlarging
c-MOFs,
opening
pathways
developing
MOF-based
The Innovation,
Journal Year:
2024,
Volume and Issue:
5(5), P. 100662 - 100662
Published: June 21, 2024
The
past
century
has
witnessed
the
flourishing
of
organic
radical
chemistry.
Stable
radicals
are
highly
valuable
for
quantum
technologies
thanks
to
their
inherent
room
temperature
coherence,
atomic-level
designability,
and
fine
tunability.
In
this
comprehensive
review,
we
highlight
potential
stable
as
high-temperature
qubits
explore
applications
in
information
science,
which
remain
largely
underexplored.
Firstly,
summarize
known
spin
dynamic
properties
examine
factors
that
influence
electron
relaxation
decoherence
times.
This
examination
reveals
design
principles
optimal
operating
conditions.
We
further
discuss
integration
solid-state
materials
surface
structures,
present
state-of-the-art
computing,
memory,
sensing.
Finally,
analyze
primary
challenges
associated
with
provide
tentative
insights
future
research
directions.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(47), P. 32161 - 32205
Published: Nov. 18, 2024
Covalent
organic
frameworks
(COFs)
are
created
by
the
condensation
of
molecular
building
blocks
and
nodes
to
form
two-dimensional
(2D)
or
three-dimensional
(3D)
crystalline
frameworks.
The
diversity
with
different
properties
functionalities
large
number
possible
framework
topologies
open
a
vast
space
well-defined
porous
architectures.
Besides
more
classical
applications
materials
such
as
absorption,
separation,
catalytic
conversions,
interest
in
optoelectronic
COFs
has
recently
increased
considerably.
electronic
both
their
linkage
chemistry
can
be
controlled
tune
photon
absorption
emission,
create
excitons
charge
carriers,
use
these
carriers
photocatalysis,
luminescence,
chemical
sensing,
photovoltaics.
In
this
Perspective,
we
will
discuss
relationship
between
structural
features
properties,
starting
connectivity,
layer
stacking
2D
COFs,
control
over
defects
morphology
including
thin
film
synthesis,
exploring
theoretical
modeling
structural,
electronic,
dynamic
discussing
recent
intriguing
focus
on
photocatalysis
photoelectrochemistry.
We
conclude
some
remarks
about
present
challenges
future
prospects
powerful
architectural
paradigm.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 27, 2025
Two-dimensional
conjugated
metal-organic
frameworks
(2D
c-MOFs)
have
emerged
as
an
intriguing
class
of
quantum
materials
due
to
their
high
crystallinity,
persistent
spin
centers,
and
tunable
structures
topologies.
However,
it
remains
unclear
how
achieve
long
relaxation
time
at
room
temperature
in
2D
c-MOFs
via
a
bottom-up
design
strategy.
Herein,
we
hexahydroxytrithiatruxene
ligand
(HHTH)
minimize
the
influence
nuclear
on
electron
while
weakening
d-π
conjugation
construct
"spin
docking"
for
preserving
which
enables
resulting
c-MOFs,
Ni3HHTH2,
exhibit
coherence
Rabi
oscillations
temperature.
Spin
dynamics
studies
not
only
reveal
unusual
temperature-dependent
frequency
Ni3HHTH2
but
also
indicate
that
coordination
mode
determines
spin-lattice
behavior
spin-phonon
coupling.
These
investigations
provide
general
guideline
development
high-performance
qubits
based
arrays.
Accounts of Chemical Research,
Journal Year:
2024,
Volume and Issue:
57(14), P. 1985 - 1996
Published: July 4, 2024
ConspectusTwo-dimensional
conjugated
metal-organic
frameworks
(2D
c-MOFs)
have
emerged
as
a
novel
class
of
multifunctional
materials,
attracting
increasing
attention
due
to
their
highly
customizable
chemistry
yielding
programmable
and
unprecedented
structures
properties.
In
particular,
over
the
past
decade,
synergistic
relationship
between
conductivity
porosity
2D
c-MOFs
has
paved
way
toward
widespread
applications.
Despite
promising
potential,
majority
yet
achieve
atomically
precise
crystal
structures,
hindering
full
understanding
control
electronic
structure
intrinsic
charge
transport
characteristics.
When
modulating
properties
two-dimensional
layered
framework
decoupling
processes
within
in
layers
is
paramount
importance,
it
represents
significant
challenge.
Unfortunately,
systems
developed
so
far
failed
address
such
major
research
target,
which
can
be
achieved
solely
by
manipulating
c-MOFs.
offer
advantage
organic
radical
molecules
covalent
frameworks:
polymerization
through
oxidative
coordination
viable
route
form
"spin-concentrated
assemblies".
However,
role
these
spin
centers
still
poorly
understood,
dynamics
spins
seldom
been
investigated.
Consequently,
overcoming
challenges
essential
unlock
potential
electronics
other
related
fields,
new
type
quantum
materials.In
this
Account,
we
summarize
discuss
our
group's
efforts
at
atomic
level
applications
spintronics,
thereby
providing
distinct
evidence
on
platform
for
exploring
phenomena.
First,
unravel
key
played
rational
design
ligands
decrease
boundary
defects,
large
single
crystals,
investigate
The
advantages
disadvantages
current
structural
elucidation
strategies
will
discussed.
Second,
fundamental
challenge
c-MOF
studies
decouple
in-plane
interlayer
pathways
tuning
To
challenge,
propose
concept
second-generation
ligands,
termed
"programmable
ligands",
replace
first-generation
lack
modifiability
they
mainly
consist
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
146(1), P. 1089 - 1099
Published: Dec. 29, 2023
The
photogeneration
of
multiple
unpaired
electron
spins
within
molecules
is
a
promising
route
to
applications
in
quantum
information
science
because
they
can
be
initialized
into
well-defined,
multilevel
states
(S
>
1/2)
and
reproducibly
fabricated
by
chemical
synthesis.
However,
coherent
manipulation
these
spin
difficult
realize
typical
molecular
systems
due
the
lack
selective
addressability
short
coherence
times
transitions.
Here,
challenges
are
addressed
using
donor–acceptor
single
cocrystals
composed
pyrene
naphthalene
dianhydride
host
spatially
oriented
triplet
excitons,
which
exhibit
photogenerated
qutrit
properties.
Time-resolved
paramagnetic
resonance
(TREPR)
spectroscopy
demonstrates
that
orienting
excitons
crystal
platform
imparts
narrow,
well-resolved,
tunable
resonances
EPR
spectrum,
allowing
sublevel
Pulse-EPR
reveals
at
temperatures
above
30
K,
decoherence
driven
exciton
diffusion.
limited
electronic
dipolar
coupling
below
where
T2
varies
nonlinearly
with
optical
excitation
density
annihilation.
Overall,
an
optimized
time
=
7.1
μs
20
K
achieved.
These
results
provide
important
insights
designing
solid-state
excitonic
materials
improved
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(47), P. 25903 - 25909
Published: Nov. 14, 2023
An
important
criterion
for
quantum
operations
is
long
qubit
coherence
times.
To
elucidate
the
influence
of
molecular
structure
on
times
spin
qubits
and
qudits,
a
series
molecules
featuring
perylenediimide
(PDI)
chromophores
covalently
linked
to
stable
nitroxide
radicals
were
synthesized
investigated
by
pulse
electron
paramagnetic
resonance
spectroscopy.
Photoexcitation
PDI
in
these
systems
creates
an
excited
quartet
state
(Q)
followed
spin-polarized
doublet
ground
(D0),
which
hold
promise
as
qudits
qubits,
respectively.
By
tailoring
qudit/qubit
candidates
selective
deuteration
eliminating
intramolecular
motion,
Tm
=
9.1
±
0.3
4.2
μs
at
85
K
D0
Q,
respectively,
are
achieved.
These
represent
nearly
3-fold
enhancement
compared
those
initial
design.
This
approach
offers
rational
structural
design
protocol
effectively
extending
qudits/qubits.
Advanced Optical Materials,
Journal Year:
2024,
Volume and Issue:
12(18)
Published: May 17, 2024
Abstract
The
intrinsic
quantum
nature
of
molecules
opens
exciting
opportunities
for
developing
the
field
information
science.
In
this
context,
porphyrins
stand
out
as
ideal
building
blocks
technologies
thanks
to
their
unique
optical
and
electrical
properties
well
capacity
accommodate
metal
atoms
ions.
This
review
bridges
chemistry
physics
porphyrins,
providing
an
overview
recent
advances
in
porphyrin‐based
molecular
qubits.
Starting
from
qubits,
explores
potential
porphyrin
units
combine,
leading
formation
logic
gates
hierarchical
higher‐dimensional
structures.
Next,
exploitation
porphyrins'
photophysical
realizing
long‐lived
high
spin
states
is
examined.
These
are
promising
photogeneration
multi‐level
systems
initialization
control
With
a
critical
eye
on
current
state‐of‐the‐art,
elucidates
future
perspectives
advancing
technologies.