Abstract
Biological
macromolecules
exhibit
emergent
functions
through
hierarchical
self‐assembly,
a
concept
that
is
extended
to
design
artificial
supramolecular
assemblies.
Here,
the
first
example
of
breaking
common
parallel
arrangement
capsule‐shaped
zirconium
coordination
cages
reported
by
constructing
porous
framework
ZrR‐1
.
adopts
quaternary
structure
resembling
protein
and
contains
12‐connected
chloride
clusters,
representing
highest
connectivity
for
zirconium‐based
thus
far.
Compared
ZrR‐2
,
demonstrated
enhanced
stability
in
acidic
aqueous
solutions
tenfold
increase
BET
surface
area
(879
m
2
g
−1
).
also
exhibits
excellent
proton
conductivity,
reaching
1.31
×
10
−2
S·cm
at
353
K
98%
relative
humidity,
with
low
activation
energy
0.143
eV.
This
finding
provides
insights
into
controlling
self‐assembly
metal–organic
discover
superstructures
properties.
Chemical Reviews,
Год журнала:
2022,
Номер
122(6), С. 6374 - 6458
Опубликована: Фев. 8, 2022
Lanthanide
supramolecular
chemistry
is
a
fast
growing
and
intriguing
research
field
due
to
the
unique
photophysical,
magnetic,
coordination
properties
of
lanthanide
ions
(LnIII).
Compared
with
intensively
investigated
mononuclear
Ln-complexes,
polymetallic
assemblies
offer
more
structural
superiority
functional
advantages.
In
recent
decades,
significant
progress
has
been
made
in
polynuclear
supramolecules,
varying
from
evolution
luminescent
magnetic
materials.
This
review
summarizes
design
principles
ligand-induced
coordination-driven
self-assembly
Ln-structures
intends
guidance
for
construction
elegant
Ln-based
architectures
optimization
their
performances.
Design
concerning
water
solubility
chirality
lanthanide-organic
that
are
vital
extending
applications
emphasized.
The
strategies
improving
up-conversion,
host–guest
chemistry,
sensing,
catalysis
have
summarized.
Magnetic
materials
based
on
assembled
given
an
individual
section
classified
features.
Challenges
remaining
perspective
directions
this
also
briefly
discussed.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(9), С. 4244 - 4253
Опубликована: Фев. 23, 2022
Chiral
luminescent
lanthanide–organic
cages
have
many
potential
applications
in
enantioselective
recognition,
sensing,
and
asymmetric
catalysis.
However,
due
to
the
paucity
of
structures
their
limited
cavities,
host–guest
chemistry
with
has
remained
elusive
so
far.
Herein,
we
report
a
guest-driven
self-assembly
chiral
induction
approach
for
construction
otherwise
inaccessible
Ln4L4-type
(Ln
=
lanthanide
ions,
i.e.,
EuIII,
TbIII;
L
ligand)
tetrahedral
hosts.
Single
crystal
analyses
on
series
complexes
reveal
remarkable
guest-adaptive
cavity
breathing
cages,
reflecting
advantage
variation
tolerance
coordination
geometry
f-elements.
Meanwhile,
noncovalent
confinement
pyrene
within
cage
not
only
leads
diminishment
its
excimer
emission
but
also
facilitates
guest
host
energy
transfer,
opening
up
new
sensitization
window
luminescence
cage.
Moreover,
stereoselective
either
Λ4-
or
Δ4-
type
Eu4L4
been
realized
via
R/S-BINOL
R/S-SPOL
templates,
as
confirmed
by
NMR,
circular
dichroism
(CD),
circularly
polarized
(CPL)
high
dissymmetry
factors
(glum)
±0.125.
Chemical Society Reviews,
Год журнала:
2022,
Номер
51(12), С. 5101 - 5135
Опубликована: Янв. 1, 2022
This
review
highlights
transformation
networks
created
with
coordination
cages.
Such
synthetic
stimuli-controlled
can
help
elucidate
biological
signal
transduction,
as
well
enabling
new
functions
and
applications.
Chemical Society Reviews,
Год журнала:
2022,
Номер
51(8), С. 2957 - 2971
Опубликована: Янв. 1, 2022
Although
metallosupramolecular
cages
are
self-assembled
from
seemingly
simple
building
blocks,
metal
ions
and
organic
ligands,
architectures
of
increasingly
large
size
complexity
accessible
exploited
in
applications
catalysis
to
the
stabilisation
reactive
species.
This
Tutorial
Review
gives
an
introduction
principles
for
designing
highlights
advances
design
lower
symmetry
cages.
The
characterisation
identification
relies
on
a
number
complementary
techniques
with
NMR
spectroscopy,
mass
spectrometry,
X-ray
crystallography
computational
methods
being
focus
this
review.
Finally,
examples
discussed
where
these
put
into
practice
application
or
function
cage.
Chemical Society Reviews,
Год журнала:
2023,
Номер
53(1), С. 47 - 83
Опубликована: Окт. 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,
Год журнала:
2022,
Номер
144(35), С. 16191 - 16198
Опубликована: Авг. 16, 2022
The
selective
separation
of
structurally
similar
aliphatic/aromatic
hydrocarbons
is
an
essential
goal
in
industrial
processes.
In
this
study,
we
report
the
synthesis
a
water-soluble
(Tr2M3)4L4
(Tr
=
cycloheptatrienyl
ring;
M
metal;
L
organosulfur
ligand)
molecular
cage
(1)
via
self-assembly
acceptor
tripalladium
sandwich
species
[(Tr2Pd3)(CH3CN)][NO3]2
and
attachment
onto
solubilizing
methoxyethoxy
appendants
to
be
utilized
energy-friendly
alternative
approach
molecules
under
ambient
conditions.
Cage
1,
comprising
hydrophobic
inner
cavity,
exhibited
good
solubility
stability
aqueous
media.
It
also
demonstrated
excellent
performance
sequential
alkanes
(C6–C9),
xylene,
other
disubstituted
benzene
isomers
cis/trans-decalin.
Journal of the American Chemical Society,
Год журнала:
2021,
Номер
143(42), С. 17316 - 17336
Опубликована: Окт. 7, 2021
The
exploration
of
chiral
crystalline
porous
materials,
such
as
metal-organic
complexes
(MOCs)
or
frameworks
(MOFs),
has
been
one
the
most
exciting
recent
developments
in
materials
science
owing
to
their
widespread
applications
enantiospecific
processes.
However,
achieving
specific
tight-affinity
binding
and
remarkable
enantioselectivity
toward
important
biomolecules
is
still
challenging.
Perhaps
critically,
lack
adaptability,
compatibility,
processability
these
severely
impedes
practical
chemical
engineering
biological
technology.
In
this
Perspective,
artificial
metal-peptide
assemblies
(MPAs),
which
are
achieved
by
assembly
peptides
metals
with
nanometer-sized
cavities
pores,
a
new
development
that
could
address
current
bottlenecks
materials.
Bioinspired
pore-forming
MPAs
not
foreign
systems
granted
scientists
an
unprecedented
level
control
over
recognition
sites,
conformational
flexibility,
cavity
sizes,
hydrophilic
segments
through
ultrafine-tuning
peptide-derived
linkers.
We
will
specifically
discuss
exemplary
including
structurally
well-defined
highly
frameworks.
With
insights
from
structures,
peptide
folding
closer
cooperation
metal
coordination
noncovalent
interactions
can
create
adaptable
protein-like
nanocavities
undergoing
myriad
variations
reminiscent
enzymatic
pockets.
also
consider
challenges
advancing
field,
where
deployment
side-chain
groups
manipulation
amino
acid
sequences
more
likely
access
programmable,
genetically
encodable
peptide-mediated
thus
contributing
enhanced
enantioselective
well
enabling
key
biochemical
processes
next-generation
versatile
biomimetic
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(33)
Опубликована: Май 21, 2022
Controllable
arrangement
of
different
ligands
in
a
single
assembly
will
not
only
bring
increased
complexity
but
also
offers
new
route
to
fine-tune
the
function
designed
architecture.
We
report
here
combinatorial
self-assembly
with
enPd(NO3
)2
and
three
(L1-3
),
which
gave
rise
family
six
palladium-organic
cages
(C1-6)
systematically
varied
shapes
cavities,
including
heteroleptic
(Pd5
L12
L2
,
Pd5
L3
Pd4
one
homoleptic
(Pd4
L32
)
cages,
two
known
(Pd6
L14
L22
cages.
Emergent
functions
due
fusion
half
cavities
on
from
their
parent
have
been
observed:
can
form
ternary
complexes
by
co-encapsulation
both
aromatic
aliphatic
guests,
while
counterparts
binary
complexes.
Such
forced
effect
endows
enhanced
catalytic
power
for
Knoevenagel
condensation.
