Chemical Science,
Journal Year:
2022,
Volume and Issue:
13(18), P. 5325 - 5332
Published: Jan. 1, 2022
Discrete
nanocages
provide
a
way
to
solubilize,
separate,
and
tune
the
properties
of
fullerenes,
but
these
3D
receptors
cannot
usually
be
synthesized
easily
from
inexpensive
starting
materials,
limiting
their
utility.
Herein,
we
describe
first
fullerene-binding
nanocage
(Cage4+)
that
can
made
efficiently
on
gram
scale.
Cage4+
was
prepared
in
up
57%
yield
by
formation
pyridinium
linkages
between
complemantary
porphyrin
components
are
themselves
readily
accessible.
binds
C60
C70
with
large
association
constants
(>108
M-1),
thereby
solubilizing
fullerenes
polar
solvents.
Fullerene
redox-properties
were
subsequently
investigated
across
multiple
charge
states
host-guest
complexes.
Remarkably,
neutral
singly
reduced
bind
similar
strengths,
leaving
0/1-
redox
couples
minimally
perturbed
fully
reversible,
whereas
other
hosts
substantially
alter
fullerenes.
Thus,
C60@Cage4+
C70@Cage4+
may
useful
as
solubilized
fullerene
derivatives
preserve
inherent
electron-accepting
electron-transfer
capabilities
Fulleride
dianions
also
found
strongly
Cage4+,
while
further
reduction
is
centered
host,
leading
lowered
fulleride
guest
case
C602-.
Chemical Reviews,
Journal Year:
2022,
Volume and Issue:
122(11), P. 10393 - 10437
Published: April 18, 2022
The
field
of
metallosupramolecular
chemistry
has
advanced
rapidly
in
recent
years.
Much
work
this
area
focused
on
the
formation
hollow
self-assembled
metal-organic
architectures
and
exploration
applications
their
confined
nanospaces.
These
discrete,
soluble
structures
incorporate
metal
ions
as
'glue'
to
link
organic
ligands
together
into
polyhedra.Most
employed
thus
far
have
been
highly
symmetrical,
these
easiest
prepare.
Such
high-symmetry
contain
pseudospherical
cavities,
so
typically
bind
roughly
spherical
guests.
Biomolecules
high-value
synthetic
compounds
are
rarely
isotropic,
highly-symmetrical
species.
To
bind,
sense,
separate,
transform
such
substrates,
new,
lower-symmetry,
cages
needed.
Herein
we
summarize
approaches,
which
taken
form
first
draft
a
handbook
for
design
higher-complexity,
architectures.
Journal of the American Chemical Society,
Journal Year:
2020,
Volume and Issue:
142(44), P. 18763 - 18768
Published: Oct. 21, 2020
Here
we
report
two
highly
emissive
perylene
diimide
(PDI)-based
metallacages
and
explore
their
complexation
with
polycyclic
aromatic
hydrocarbons,
such
as
pyrene,
triphenylene,
perylene.
The
fluorescence
quantum
yields
of
exceed
90%
binding
constants
can
reach
high
2.41
×
104
M-1
in
acetonitrile.
These
features
enable
further
tuning
the
emission
host-guest
complexes
to
obtain
white-light
based
on
complementary
orange
blue
Moreover,
owing
huge
differences
solution
solid
state,
are
successfully
employed
for
information
encryption.
This
study
offers
a
general
approach
construction
explores
application
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(28), P. 12825 - 12833
Published: July 5, 2022
The
construction
of
supramolecular
coordination
complexes
(SCCs)
featuring
prominent
cancer
theranostic
functions
is
an
appealing
yet
significantly
challenging
task.
In
this
study,
we
rationally
designed
and
facilely
constructed
a
prism-like
metallacage
C-DTTP
with
efficient
fluorescence
emission
in
the
second
near-infrared
(NIR-II)
region
through
assembly
aggregation-induced
emission-active
four-arm
ligand
90°
Pt
acceptors
Pt(PEt3)2(OTf)2.
held
longest
maximum
wavelength
(1005
nm)
compared
those
previously
reported
SCCs
up
to
now
exhibited
both
high
photothermal
conversion
efficiency
(39.3%)
superior
reactive
oxygen
species
generation
behavior
precursor
ligand.
vitro
vivo
assessments
demonstrated
that
metallacage-loaded
nanoparticles
excellent
biocompatibility
stability
were
capable
simultaneously
affording
precise
tumor
diagnosis
complete
elimination
by
means
NIR-II
fluorescence/photothermal
dual
imaging-guided
photodynamic/photothermal
synergistic
therapy.
Chemical Society Reviews,
Journal Year:
2023,
Volume and Issue:
53(1), P. 47 - 83
Published: Oct. 18, 2023
We
review
recent
work
at
the
interface
of
supramolecular
chemistry
and
fullerene
chemistry.
focus
on
selective
functionalization,
host–guest
chemistry,
non-covalent
dyads,
mechanically
interlocked
architectures
2D/3D
assemblies.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(14), P. 7692 - 7711
Published: March 28, 2023
Self-assembled
discrete
molecular
architectures
that
show
selective
recognition
within
their
internal
cavities
are
highly
desirable.
Such
hosts
often
guest
through
several
noncovalent
interactions.
This
emulates
the
activity
of
naturally
occurring
enzymes
and
proteins.
Research
in
formation
3D
cages
different
shapes
sizes
has
progressed
rapidly
since
development
coordination-driven
self-assembly
dynamic
covalent
chemistry.
find
applications
catalysis,
stabilization
metastable
molecules,
purification
isomeric
mixtures
via
encapsulation,
even
biomedical
applications.
Most
these
stem
from
ability
host
to
bind
guests
strongly
a
fashion,
providing
suitable
environment
for
perform
functions.
Molecular
having
closed
with
small
windows
either
poor
encapsulation
or
inhibit
easy
release
while
those
wide
open
structures
fail
form
stable
host-guest
complexes.
In
this
context,
barrels
obtained
by
metal-ligand/covalent
bond
techniques
possess
optimized
architectures.
With
hollow-walled
cavity
two
large
openings,
satisfy
structural
requirements
many
perspective,
we
will
discuss
detail
synthetic
strategies
obtaining
barrel-like
employing
coordination
interactions,
structure-based
classification,
storing
transient
separation
chemicals,
photoinduced
antibacterial
activity.
We
aim
highlight
advantages
over
other
efficiently
carrying
out
functions
new
Angewandte Chemie International Edition,
Journal Year:
2021,
Volume and Issue:
60(25), P. 14109 - 14116
Published: April 9, 2021
Fullerene
extracts
obtained
from
fullerene
soot
lack
their
real
application
due
to
poor
solubility
in
common
solvents
and
difficulty
purification.
Encapsulation
of
these
a
suitable
host
is
an
important
approach
address
issues.
We
present
new
Pd6
barrel
(1),
which
composed
three
1,4-dihydropyrrolo[3,2-b]pyrrole
panels,
clipped
through
six
cis-PdII
acceptors.
Large
open
windows
cavity
make
it
efficient
for
large
guest.
Favorable
interactions
between
the
ligand
(C60
C70
)
allows
encapsulate
efficiently.
Thorough
investigation
reveals
that
1
has
stronger
binding
affinity
towards
over
C60
,
resulting
predominant
extraction
mixture
two.
Finally,
encapsulated
barrels
⊂1
were
found
be
visible-light-induced
singlet
oxygen
generation.
Such
preferential
photosensitizing
ability
are
noteworthy.
Angewandte Chemie International Edition,
Journal Year:
2020,
Volume and Issue:
60(9), P. 4705 - 4711
Published: Nov. 30, 2020
Self-assembly
by
imine
condensation
in
aqueous
media
is
a
formidable
task
because
of
the
labile
nature
imines
presence
water.
Here,
taking
advantage
multivalence
and
ligand
preorganization,
basket-shaped
triscationic
cage
molecules
are
self-assembled
high
yields
both
water
organic
solvent,
condensing
hexaformyl
bisamine.
These
cages,
especially
chiral
ones,
stable
or
inert
solution,
that
is,
no
decomposition
was
observed
upon
dilution,
precipitation,
exposure
to
competitive
amines
aldehydes.
Such
water-compatibility
allows
hosts
take
hydrophobic
effect
accommodate
guests.
The
S-23+
selectively
binds
distinguishes
one
two
enantiomers,
opening
up
opportunities
for
applications
such
as
compound
separation.
Chiral
narcissistic
self-sorting
sergeants-and-soldiers
effects
occur
during
formation
when
amino
precursors
involved
self-assembly.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(19), P. 8778 - 8788
Published: May 4, 2022
Supramolecular
cage
chemistry
is
of
lasting
interest
because,
as
artificial
blueprints
natural
enzymes,
the
self-assembled
structures
not
only
provide
substrate-hosting
biomimetic
environments
but
also
can
integrate
active
sites
in
confined
nanospaces
for
function
synergism.
Herein,
we
demonstrate
a
vertex-directed
organic-clip
chelation
assembly
strategy
to
construct
metal–organic
Fe4L68+
(MOC-63)
incorporating
12
imidazole
proton
donor–acceptor
motifs
and
four
redox-active
Fe
centers
an
octahedral
coordination
nanospace.
Different
from
regular
supramolecular
cages
assembled
with
metal
vertices,
MOC-63
comprises
six
ditopic
ligands
vertices
tris-chelating
Fe(N∩N)3
moieties
faces,
thus
improving
its
acid,
base,
redox
robustness
by
virtue
cage-stabilized
dynamics
solution.
Improved
dehydrogenation
catalysis
1,2,3,4-tetrahydroquinoline
derivatives
accomplished
owing
effect
that
synergizes
multiple
radical
species
expedite
intermediate
conversion
multistep
reactions
cage-confined
The
acid–base
buffering
play
vital
role
modulating
total
charge
state
resist
pH
variation
tune
solubility
among
varied
solvents,
thereby
enhancing
reaction
acceleration
acidic
conditions
rendering
facile
recycling
catalytic
process.
Angewandte Chemie International Edition,
Journal Year:
2021,
Volume and Issue:
60(33), P. 17904 - 17909
Published: May 26, 2021
Abstract
Organic
cages
are
fascinating
because
of
their
well‐defined
3D
cavities,
excellent
stability,
and
accessible
post‐modification.
However,
the
synthesis
is
normally
realized
by
fragment
coupling
approach
in
low
yields.
Herein,
we
report
one‐pot,
gram‐scale
shape‐controlled
two
covalent
organic
(box‐shaped
[4]cage
triangular
prism‐shaped
[2]cage)
yields
46
%
52
%,
involving
direct
condensation
1,3,5‐tris(2,4‐dimethoxyphenyl)benzene
monomer
with
paraformaldehyde
isobutyraldehyde,
respectively.
The
can
convert
into
high‐yielding
per‐hydroxylated
analogues.
[2]cage
be
utilized
as
gas
chromatographic
stationary
phase
for
high‐resolution
separation
benzene/cyclohexane
toluene/methylcyclohexane.
By
changing
central
moiety
and/or
aldehyde,
this
synthetic
method
would
have
potential
to
a
general
strategy
access
diverse
tunable
shape,
size,
electronic
properties.
Energy & Environmental Science,
Journal Year:
2021,
Volume and Issue:
15(2), P. 780 - 785
Published: Dec. 22, 2021
A
charge-separated
and
redox-active
C
60
@porous
organic
cage
(C
@POC)
compound
was
synthesized
to
act
as
the
cathode
in
a
photo-assisted
Li-organic
battery,
which
enables
efficient
solar
electrochemical
energy
conversion
storage.