Abstract
We
describe
effective
development
of
the
highly
diastereoselective
synthesis
double
helical
tetraamine
2-H2-C2
and
propose
a
mechanism
for
its
formation.
The
resolution
is
facilitated
by
high
racemization
barrier
43
kcal
mol–1
it
implemented
via
either
chiral
auxiliary
or
preparative
supercritical
fluid
chromatography.
This
enables
preparation
first
high-spin
neutral
diradical,
with
spin
density
delocalized
within
an
enantiomeric
π-system.
presence
two
3-electron
C–N
bonds
in
diradical
leads
to:
(1)
triplet
(S
=
1)
ground
state
singlet-triplet
energy
gap
0.4
(2)
long
half-life
up
to
6
days
2-MeTHF
at
room
temperature.
possesses
least
26
293
K
chiroptical
properties,
absorption
anisotropy
factor
|g|
≈
0.005
548
nm.
These
unique
magnetic
optical
properties
our
form
basis
next-generation
spintronic
devices.
1
Introduction
2
Synthesis
Resolution
C
2-Symmetric
Double
Helical
Tetraamine
2-H2-C
3
Characterization
Neutral
High-Spin
Aminyl
Diradical
22•
-C
4
Conclusion
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(47), С. 32582 - 32594
Опубликована: Ноя. 13, 2024
Near-infrared
II
(NIR-II)
phototheranostic
agents
have
become
prominent
for
the
early
diagnosis
and
precise
treatment
of
cancer.
Organic
open-shell
diradicaloids
with
distinct
structure
narrow
band
gap
are
promising
candidates
phototherapeutic
due
to
their
strong
spin-coupling
effect
NIR
light-harvesting
capacity.
However,
achieving
stable
efficient
NIR-II
luminescent
is
crucial
yet
rather
challenging
considering
high
chemical
reactivity
self-absorption.
Herein,
two
highly
diradicaloids,
2PhNVDPP
PhNVDPP,
were
successfully
fabricated
by
employing
an
acceptor
planarization/π-conjugation
extension
donor
rotation
strategy.
After
encapsulation
into
water-dispersible
nanoparticles
(NPs),
NPs
exhibit
luminescence,
PCE
53%,
improved
photo/heat
stability.
In
vivo
experiments
demonstrated
clear
visualization
blood
vessels
tumors,
as
well
successful
imaging-guided
photothermal
ablation
tumors.
This
study
not
only
develops
a
pioneering
diradicaloid
agent
luminescence
but
also
provides
unique
perspective
effectiveness
multimodal
anticancer
therapy.
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 19, 2025
Polycyclic
aromatic
hydrocarbons
(PAHs)
with
open-shell
or
redox
characteristics
are
highly
desirable
due
to
their
intriguing
electronic
properties
and
potential
applications.
Here,
we
demonstrate
a
series
of
phenylenediamine-linked
nanographenes
(NGs)
1–3
by
connecting
two
aza-hexa-peri-hexabenzocoronene
(HBC)
units
p-phenylene,
p,p'-biphenylene,
p,p"-terphenylene,
respectively,
unveil
3D
conformations,
structures,
properties.
As
proved
X-ray
crystallographic
analysis
quantum
chemical
calculation,
adopted
anti-folded,
Z-shaped
structures
rotatable
single
bonds.
The
structure-dependent
capabilities
were
disclosed.
For
1,
stable
monoradical
cation
was
generated
one-electron
oxidation
as
the
terminal
product.
revealed
an
unprecedented
syn-folded
structure
1+.
However,
2
3
demonstrated
redox-active
molecules
from
neutral
dication
that
each
oxidative
state
can
be
precisely
controlled
oxidation/reduction.
Chemical Communications,
Год журнала:
2024,
Номер
60(68), С. 8997 - 9006
Опубликована: Янв. 1, 2024
Spin
properties
are
intrinsic
characters
of
electrons.
Radical
molecules
contain
unpaired
electron(s),
and
their
unique
chemical
physical
make
them
an
ideal
platform
for
investigating
spin
in
molecular
systems.
Among
them,
the
burgeoning
interest
stable
conjugated
diradicals
is
attributed
to
distinctive
characteristics,
notably
dynamic
resonance
structures
between
open-shell
closed-shell
forms,
malleability
states,
profound
influence
intermolecular
spin-spin
interactions.
A
deep
understanding
characteristics
electrons
provides
guidance
design,
synthesis,
characterization
radical-based
materials.
In
this
review,
we
discuss
delocalization,
coupling
emphasize
how
precisely
control
these
understand
role
as
functional
radical
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(38), С. 26454 - 26465
Опубликована: Сен. 10, 2024
Dimerization
of
delocalized
polycyclic
hydrocarbon
radicals
is
a
simple
and
versatile
method
to
create
diradicals
with
tailored
electronic
structures
accessible
high-spin
states.
However,
the
synthesis
challenging,
stability
issue
remains
concern.
In
this
study,
we
present
stable
non-Kekulé
1,1'-biolympicenyl
diradical
Chemistry of Materials,
Год журнала:
2024,
Номер
unknown
Опубликована: Авг. 14, 2024
Molecular
topology
synthesis
of
polycyclic
aromatic
hydrocarbons
(PAHs)
with
diradical
character
takes
root
in
intramolecular
coupling
breakthrough.
Herein,
we
report
selective
Mn(III)/Cu(II)-mediated
C–P
and
C–H
bond
cleavage
to
obtain
robust
donor-fused
phosphoniums
helical
or
planar
geometries
distinct
cationic
charges.
The
former
structures
incorporate
a
common
phospha[5]helication
acceptor
different
arylamine
donors,
the
latter
structure
contains
phospha[6]dication
same
donors.
These
unprecedented
ionic
salts
hold
distinguishing
donor–acceptor
(D–A)
constructions,
showing
unique
topology-dependent
optoelectronic
properties.
folded
radical
ammoniums
possess
an
extreme
electron-deficient
state
through-space
isolation
high
(y0
=
0.989).
Moreover,
tunable
charge
transfer
(CT)
locally
excited
(LE)
transition
components
facilitate
diverse
hybridized
local
(HLCT)
solvents,
endowing
highest
emission
band
gap
variation
0.78
eV
(∼217
nm).
fluorescence
radiation
could
also
be
adjusted
from
blue
near-infrared
regions
via
tailoring
polar-dependent
states,
which
output
additional
circularly
polarized
luminescence
compatible
chiral
menthol
matrix
elevated
quantum
efficiency
undisturbed
deep-red
glow.
It
is
worth
mentioning
that
atomically
precise
Mn(III)
halide
has
been
unprecedentedly
captured
determined
for
activation.
Advanced Functional Materials,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 15, 2024
Abstract
Extensive
research
over
recent
decades
has
demonstrated
the
feasibility
of
producing
stable
radical
polymers
(SRPs)
by
exploring
structure–stability
relationships.
Owing
to
their
excellent
redox
activities
and
inherent
paramagnetic
characteristics,
SRPs
are
emerging
as
key
functional
materials
with
considerable
potentials
for
various
applications
such
in
organic
electrodes,
semiconductors,
magnetic
materials,
quantum
information
technologies.
Accordingly,
this
review
provides
a
comprehensive
summary
most
widely
investigated
representative
families
SRPs.
Innovative
strategies
design
synthesis
relationship
among
physicochemical
properties,
electronic
structures,
resulting
functionalities
these
discussed.
Moreover,
advancements
highlighted.
Finally,
challenges
chemistry
material
functionalization,
offering
insights
into
transformative
potential
future
applications,
emphasized.
Chemical Science,
Год журнала:
2024,
Номер
15(33), С. 13343 - 13350
Опубликована: Янв. 1, 2024
The
unique
optical
and
magnetic
properties
of
organic
biradicaloids
on
polycyclic
aromatic
hydrocarbons
are
fundamental
interest
in
the
development
novel
optoelectronic
materials.
