Abstract
We
herein
report
the
facile
synthesis
of
two
helical
carbon
nanorings
with
small
ring
sizes,
cyclo[6]paraphenylene‐1,5‐naphthylene
(
[6]CPPNap
1,5
),
and
cyclo[6]paraphenylene‐1,5‐anthrylene
[6]CPPAn
).
The
structures
were
determined
by
NMR
HR‐MS.
X‐ray
single‐crystal
data
was
also
achieved.
strain
energy
racemization
processes
investigated
DFT
calculations.
reduced
sizes
result
in
increased
elevated
barriers.
photophysical
properties
studied
UV‐Vis
absorption,
fluorescence
emission,
time‐resolved
decay.
Nature Communications,
Год журнала:
2025,
Номер
16(1)
Опубликована: Янв. 7, 2025
Developing
donor-acceptor
[n]cycloparaphenylenes
(D-A
[n]CPPs)
with
multiple
emissions
from
different
emissive
states
remains
challenging
yet
crucial
for
achieving
white-light
emission
in
single-molecule.
Here,
we
report
our
explorations
into
acceptor
engineering
of
quinone-based
D-A
[10]CPPs
(Nq/Aq/Tq[10]CPPs)
via
a
post-lateral
annulation
using
Diels-Alder
reactions
oxTh[10]CPP.
X-ray
analysis
reveals
that
Nq[10]CPP
displays
side
by
packing
naphthoquione
stacking
while
Aq[10]CPP
adopts
an
intercalated
conformation
through
anthraquinone
interaction.
Fluorescence
investigations
reveal
the
display
distinctive
acceptor-dependent
dual-emission
both
locally
excited
state
and
charge
transfer
after
single-wavelength
excitation
organic
solvents,
consequently
leading
to
multicolor
emissions,
particular,
CHCl3
Aq[10]CPP.
In
THF/water
mixture,
oxTh[10]CPP
wide
range
fluorescence
including
as
increasing
fraction
water,
accompanying
formation
nanoparticles
demonstrated
Tyndall
effect
SEM.
Interestingly,
can
be
switched
white
blue
upon
redox.
Our
demonstrate
not
only
endows
two
distint
but
also
highlights
effective
post-synthetic
strategy
functionalizing
CPP
nanohoops
desirable
properties.
authors
yield
emission.
Advanced Optical Materials,
Год журнала:
2024,
Номер
12(18)
Опубликована: Май 20, 2024
Abstract
Molecular
chirality
plays
a
pivotal
role
across
the
disciplines
of
chemical
and
physical
sciences,
as
well
holding
significant
implications
in
realms
medicine
technology.
Chiral
macrocycles
have
attracted
recent
interests
synthetic
chemistry,
material
science,
supramolecular
chemistry.
Due
to
cyclic
arrangements
stereogenic
elements
or
special
orientations
confined
rigid
structures,
π‐conjugated
chiral
are
expected
be
highly
luminescent,
configurationally
stable,
thus
serve
develop
high‐performance
chiroptical
materials.
Given
rapid
progress
achieved
this
new
area
years,
it
is
highlight
concepts
breakthroughs.
This
minireview
will
offer
overview
wide
range
from
traditional
molecules
which
include
axially,
helically,
planar
skeletons
nanobelts
with
focus
on
structure‐function
relationship
between
unique
properties.
Chemical Communications,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
In
this
review,
we
summarize
five
different
types
of
pillar[5]arene-based
nanomaterials
and
their
applications
in
chemotherapy,
photodynamic
therapy,
photothermal
multimodal
synergistic
therapy
for
tumors.
JACS Au,
Год журнала:
2024,
Номер
4(2), С. 402 - 410
Опубликована: Янв. 22, 2024
We
presented
the
construction
of
ring-in-ring
and
Russian
doll
complexes
on
basis
triptycene-derived
carbon
nanoring
(TP-[12]CPP),
which
not
only
acts
as
a
host
for
pillar[5]arene
(P5A)
but
also
serves
an
energy
donor
building
Förster
resonance
transfer
(FRET)
systems.
demonstrated
that
their
hierarchical
assembly
processes
could
be
efficiently
monitored
in
real
time
using
FRET.
NMR,
UV–vis
fluorescence,
mass
spectroscopy
analyses
confirmed
successful
encapsulation
guests
P5A/P5A-An
by
TP-[12]CPP,
facilitated
C–H···π
···π
interactions,
resulting
formation
distinct
complex
with
binding
constant
Ka
=
2.23
×
104
M–1.
The
encapsulated
can
further
reverse
its
role
to
acceptors
form
complexes,
evidenced
occurrence
FRET
analyses.
apparent
was
up
3.6
M–1,
thereby
suggesting
enhanced
synergistic
effect.
Importantly,
exhibited
both
intriguing
one-step
sequential
dependent
subcomponent
during
assembly,
reminiscent
structure
light-harvesting
system
purple
bacteria.
The
carbon
nanorings,
possessing
a
radial
π
system,
have
garnered
significant
attention
primarily
due
to
their
size-dependent
photophysical
properties
and
the
presence
of
unique
curved
π-conjugated
cavity.
This
is
evidenced
by
rapid
proliferation
publications.
Furthermore,
integration
building
blocks
into
CPP
skeletons
can
confer
[n]CPPs
with
novel
exceptional
electronic
characteristics,
as
well
chiral
host-guest
interactions,
thereby
augmenting
diversity
[n]CPPs.
Notably,
surface
structures
concave
cavity
nanorings
enable
them
host
aromatic
or
non-aromatic
guests
complementarily
surface,
resulting
in
interesting
binary
ternary
complexes.
review
provides
comprehensive
treatment
literature
reports
on
complexes,
focusing
both
interactions
properties.
It
important
note
that
scope
this
limited
chemistry
complexes
based
nanorings.
Abstract
Chiral
carbon
nanohoops
with
both
high
fluorescence
quantum
yield
and
large
luminescence
dissymmetry
factor
are
essential
to
the
development
of
circularly
polarized
(CPL)
materials.
Herein,
rational
design
synthesis
a
series
highly
fluorescent
chiral
TP‐[8–13]CPPs
via
symmetry
breaking
triptycene
motif
is
reported.
Theoretical
calculations
revealed
that
causes
unique
size‐dependent
localization
in
highest
occupied
molecular
orbitals
(HOMOs)
lowest
unoccupied
obtitals
(LUMOs)
as
increasing
sizes,
which
sharply
different
from
those
[n]cycloparaphenylenes.
Photophysical
investigations
demonstrated
TP‐[n]CPPs
display
emissions
yields
up
92.9%
for
TP‐[13]CPP,
value
among
reported
conjugated
nanohoops.
The
presumably
attributed
acyclic,
radial
conjugations
radiative
transition
rates,
further
supported
by
theoretical
investigations.
Chiroptical
studies
exhibit
bright
CPL
brightness
100.5
M
−1
cm
TP‐[11]CPP
due
yield.
Importantly,
intrigued
properties
regards
(chir)optical
properties,
follow
nice
linear
relationship
versus
1/n.
Such
not
observed
other
including
CPPs.
Chemical Communications,
Год журнала:
2024,
Номер
60(64), С. 8387 - 8390
Опубликована: Янв. 1, 2024
Nano-assemblies
based
on
perphenazine
modified
pillar[5]arene
were
constructed
successfully
for
synergistic
photothermal
and
photodynamic
(I&II)
cancer
therapy.
ACS Applied Materials & Interfaces,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 9, 2025
Designing
the
architecture
of
donor–acceptor
(D–A)
pairs
is
an
effective
strategy
to
tailor
electronic
structure
conjugated
macrocycles
for
optoelectronic
devices.
Herein,
we
present
synthesis
three
D–A
nanohoops
NDI-[n]CPP
(n
=
7,
8,
9)
containing
a
naphthalene
diimide
(NDI)
unit
as
acceptor
and
[n]cycloparaphenylenes
([n]CPPs)
moieties
donors.
The
characteristics
NDI-[7–9]CPPs
were
substantiated
through
absorption
fluorescence
spectroscopic
studies,
electrochemical
investigations,
computational
analysis.
device
investigations
demonstrated
that
can
serve
photoconductive
layer
demonstrate
significant
generation
photocurrent
with
fast
response
upon
exposure
light.
magnitude
shows
high
dependence
on
size
their
rings,
increasing
tendency
ring
decreases.
in
free
acceptor-based
CPP
has
rarely
been
reported
previous
literature.
Significantly,
C60
complexes
exhibited
marked
enhancement
under
identical
conditions;
particular,
C60⊂NDI-[7]CPP
ca.
3.5
times
greater
than
NDI-[7]CPP
alone.
Furthermore,
potential
applications
electron-
hole-transport
devices
have
also
explored,
revealing
clear
evidence
bipolar
behavior
active
charge
transport
layer.
Chinese Journal of Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 21, 2025
Comprehensive
Summary
Traditional
fluorescent
probes
typically
display
blueshifted
emission
in
rigidifying
media;
however,
a
newly
developed
class
of
rigidochromic
fluorophores
derived
from
phenanthridine
demonstrates
remarkable
redshifted
under
similar
conditions.
Pyridine,
with
N‐heterostructure
to
those
group,
is
considered
promising
candidate
for
achieving
comparable
rigidity‐induced
redshift
behavior.
In
this
work,
we
synthesized
eight
organic
featuring
diverse
functional
units
and
substitutes
by
systematically
combining
pyridine
carbazole,
triazatruxene
(TAT),
tetraphenylethylene
(TPE),
respectively.
These
molecules
exhibit
significant
redshifts
(up
225
nm,
record
high
value
ever
reported)
or
notable
intensity
changes
as
the
rigidity
polymer
matrix
increases,
along
unique
acid
responsiveness.
The
differences
polar‐π
interactions
between
polymers
diversify
behavior,
advancing
development
secure
printing
intelligent
optical
materials.
By
embedding
these
into
films
helical
phase
structures,
tunable
chirality
was
achieved.
Notably,
leveraging
acid‐responsive
properties
fluorophores,
time‐dependent
light‐controlled
dynamic
encryption
system
constructed,
successfully
enabling
multi‐level
information
encryption.
This
research
greatly
expands
scope
their
applications
anti‐counterfeiting
storage.