Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(11)
Опубликована: Янв. 16, 2023
Non-alternant
non-benzenoid
hydrocarbons
exhibit
very
different
optical
and
electronic
properties
than
their
well-studied
benzenoid
analogues.
However,
preparing
such
structures
with
extended
conjugation
length,
remains
challenging.
Herein,
we
report
the
synthesis
of
azuleno[2,1,8-ija]azulene
derivatives
using
a
two-step
sequence
involving
four-fold
aldol
condensation
between
aromatic
dialdehydes
readily
available
tetrahydropentalene-2,5-(1H,3H)-dione.
Molecules
band
gap
values
ranging
from
1.69
to
2.14
eV
molar
extinction
coefficients
(ϵ)
nearly
3×105
M-1
cm-1
have
been
prepared.
These
annulene-like
significant
diatropic
ring
currents
(aromatic),
as
supported
by
1
H
NMR
spectroscopy
DFT
calculations.
Field-effect
transistors
(OFETs)
semiconductors
charge
mobility
up
0.05
cm2
V-1
s-1
.
Chemical Society Reviews,
Год журнала:
2023,
Номер
52(4), С. 1331 - 1381
Опубликована: Янв. 1, 2023
A
comprehensive
summary
and
deep
insights
into
the
synthesis,
characterization
multi-functional
device
applications
of
n-type
ambipolar
organic
semiconductors
are
provided
in
this
study.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(3), С. 1617 - 1630
Опубликована: Янв. 10, 2023
Dipoles
are
widely
involved
in
π-π
interactions
and
central
to
many
chemical
biological
functions,
but
their
influence
on
the
strength
of
remains
unclear.
Here,
we
report
a
study
interaction
between
azulene-based,
polar
single
molecules
naphthalene-based,
nonpolar
molecules.
By
performing
scanning
tunneling
microscopy
break
junction
measurements
single-molecule
conductance,
show
that
π-stacked
dimers
formed
by
aromatic
structures
feature
higher
electrical
conductivity
mechanical
stability
than
those
Mechanical
control
both
rotational
translational
motion
reveals
sensitive
dependence
stacking
relative
alignment
dipoles.
The
antiparallel
dipoles
was
found
be
optimal
configuration
underpins
observed
enhancement
azulene-based
Density
functional
theory
calculations
further
explained
corresponding
charge
transport
efficiency.
Our
experimental
theoretical
results
dipole
moments
significantly
enhances
electronic
coupling
stacking.
In
addition,
formation
junctions,
azulene
group
experimentally
theoretically
proved
form
Au-π
contact
with
electrodes
high
This
paper
provides
evidence
interpretation
role
at
level
offers
new
insights
into
potential
applications
supramolecular
devices.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 7, 2025
Azuacenes,
defined
as
azulene
fused
with
acenes
in
a
6-7-5
ring
topology
and
spanning
lengths
from
3
to
6
rings,
have
been
synthesized
using
new
skeleton
editing
[3
+
2]
annulation
synthesis
protocol
distinction
regarding
the
procedures
obtain
6-5-7
isomers.
Comprehensive
studies
on
ground-state
excited-state
spectroscopy,
electrochemical
properties,
chemical
stability,
solid-state
structure
conducted
compare
these
azuacenes
acenes.
For
same
number
of
we
found
that
improve
stability
(i.e.,
smaller
diradical
character)
their
photophysical
properties
anti-Kasha
emissions
modulation
energy
strength
visible
bands)
but
they
reduce
transport
features
compared
those
Compared
azulene,
performance
terms
electrical
properties.
Overall,
fusion
known
polycyclic
compounds,
such
acene
produces
isomeric
hybrid
compounds
enhanced
Here,
resulting
turn
out
conserve
most
unique
two
building
blocks
associate
facility
π-delocalization
positive
charge
zwitterion
over
fragment.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(8), С. 3370 - 3375
Опубликована: Фев. 21, 2022
Bis-periazulene
(cyclohepta[def]fluorene),
which
is
an
unknown
pyrene
isomer,
was
synthesized
as
kinetically
protected
forms.
Its
triaryl
derivatives
1c–e
exhibited
the
superimposed
electronic
structures
of
peripheral,
polarized,
and
open-shell
π-conjugated
systems.
In
contrast
to
previous
theoretical
predictions,
bis-periazulene
were
in
singlet
ground
state.
Changing
aryl
group
controlled
energy
gap
between
lowest
singlet–triplet
states.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(44)
Опубликована: Июль 13, 2022
Non-alternant
non-benzenoid
π-conjugated
polycyclic
hydrocarbons
(PHs)
are
expected
to
exhibit
very
different
electronic
properties
from
the
all-benzenoid
PHs.
Herein,
we
report
synthesis
and
physical
of
three
azulene-fused
acene
molecules
(1,
2
3),
which
isoelectronic
pentacene,
hexacene
heptacene,
respectively.
X-ray
crystallographic
analysis,
NMR
spectra,
theoretical
calculations
reveal
a
localised
aromatic
backbone
comprising
all
six-
five-membered
rings
while
seven-membered
ring
remains
non-aromatic.
They
display
both
azulene
acenes
much
more
stable
than
respective
acenes.
The
dications
1,
3
were
formed
by
chemical
oxidation.
Notably,
32+
exhibited
an
open-shell
diradical
character
(y0
=30.2
%)
as
confirmed
variable-temperature
ESR
measurements,
can
be
explained
recovery
aromaticity
2,6-anthraquinodimethane
unit
annulated
with
two
tropylium
rings.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
62(10)
Опубликована: Дек. 13, 2022
Incorporating
non-hexagonal
rings
into
polycyclic
conjugated
hydrocarbons
(PCHs)
can
significantly
affect
their
electronic
and
optoelectronic
properties
chemical
reactivities.
Here,
we
report
the
first
bottom-up
synthesis
of
a
dicyclohepta[a,g]heptalene-embedded
PCH
(1)
with
four
continuous
heptagons,
which
are
arranged
in
"Z"
shape.
Compared
its
structural
isomer
bischrysene
1
R
only
hexagonal
rings,
compound
presents
distinct
antiaromatic
character,
especially
inner
heptalene
core,
possesses
clear
nature.
In
addition,
exhibits
narrower
highest
occupied
molecular
orbital
(HOMO)-lowest
unoccupied
(LUMO)
energy
gap
than
benzenoid
contrast
R,
as
verified
by
experimental
measurements
theoretical
calculations.
Our
work
reported
herein
not
provides
new
way
to
synthesize
novel
PCHs
non-alternant
topologies
but
also
offers
possibility
tune
optical
properties.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(33)
Опубликована: Июнь 14, 2022
A
modular
approach
to
azulene
building
blocks
was
developed
starting
from
readily
available
aryl-substituted
cyclopentadiene
and
ortho-haloaryl
aldehyde
by
dehydration
condensation
followed
palladium-catalyzed
C-H
coupling.
It
facilitates
the
synthesis
of
four
nonalternant
isomers
pentacene
hexacene,
namely,
dibenzo[e,g]azulene,
benzo[1,2-f
:
5,4-f']diazulene,
4,5-f']diazulene,
naphtho[2,3-f
6,7-f']diazulene,
which
exhibit
narrow
band
gaps
with
high
stability
in
addition
protonation-caused
enhanced
near-infrared
fluorescence.
We
discovered
that
these
isomers,
i)
constitutional
isomerism
influences
significantly
their
photoelectric
properties
ii)
elongation
conjugation
system
does
not
necessarily
lead
a
narrowing
gap.
Due
easy
modifiability
nonazulene
blocks,
this
strategy
can
be
extended
modularly
prepare
numerous
multiazulene-fused
aromatics.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
62(7)
Опубликована: Дек. 13, 2022
As
a
conjugated
and
unsymmetric
building
block
composed
of
an
electron-poor
seven-membered
sp2
carbon
ring
electron-rich
five-membered
ring,
azulene
its
derivatives
have
been
recognized
as
one
the
most
promising
blocks
for
novel
electronic
devices
due
to
intrinsic
redox
activity.
By
using
1,3,5-tris(4-aminophenyl)-benzene
azulene-1,3-dicarbaldehyde
starting
materials,
azulene(Azu)-based
2D
covalent
organic
framework,
COF-Azu,
is
prepared
through
liquid-liquid
interface
polymerization
strategy
first
time.
The
as-fabricated
Al/COF-Azu/indium
tin
oxide
(ITO)
memristor
shows
typical
non-volatile
resistive
switching
performance
electric
filed
induced
intramolecular
charge
transfer
effect.
Associated
with
unique
memristive
performance,
simple
convolutional
neural
network
built
image
recognition.
After
8
epochs
training,
recognition
accuracy
80
%
neutral
trained
on
larger
data
set
achieved.
