Angewandte Chemie,
Год журнала:
2024,
Номер
136(18)
Опубликована: Фев. 7, 2024
Abstract
Although
the
synthesis
of
mechanically
interlocked
molecules
has
been
extensively
researched,
selectively
constructing
homogeneous
linear
[4]catenanes
remains
a
formidable
challenge.
Here,
we
constructed
metalla[4]catenane
in
one‐step
process
through
coordination‐driven
self‐assembly
bidentate
benzothiadiazole
derivative
ligand
and
binuclear
half‐sandwich
rhodium
precursor.
The
formation
metalla[4]catenanes
was
facilitated
by
cooperative
interactions
between
strong
sandwich‐type
π‐π
stacking
non‐classical
hydrogen
bonds
components.
Moreover,
modulating
aromatic
substituents
on
precursor,
two
metalla[2]catenanes
were
obtained.
molecular
structures
these
metallacatenanes
unambiguously
characterized
single‐crystal
X‐ray
diffraction
analysis.
Additionally,
reversible
structural
transformation
metal‐catenanes
corresponding
metallarectangles
could
be
achieved
altering
their
concentration,
as
confirmed
mass
spectrometry
NMR
spectroscopy
studies.
Proceedings of the National Academy of Sciences,
Год журнала:
2024,
Номер
121(27)
Опубликована: Июнь 28, 2024
Although
mechanically
interlocked
molecules
(MIMs)
display
unique
properties
and
functions
associated
with
their
intricate
connectivity,
limited
assembly
strategies
are
available
for
synthesis.
Herein,
we
presented
a
synergistic
strategy
based
on
coordination
noncovalent
interactions
(π–π
stacking
CH⋯π
interactions)
to
selectively
synthesize
molecular
closed
three-link
chains
(
613
links),
highly
entangled
figure-eight
knots
4
knots),
trefoil
knot
knot),
Borromean
ring
2
link).
links
can
be
created
by
the
strategic
of
nonlinear
multicurved
ligands
incorporating
furan
or
phenyl
group
long
binuclear
half-sandwich
organometallic
Cp*Rh
III
(Cp*
=
η
5
-pentamethylcyclopentadienyl)
clip.
However,
utilizing
much
shorter
units
union
2,6-naphthyl-containing
ligand
led
because
increased
π–π
between
four
consecutive
stacked
layers
interactions.
Weakening
such
resulted
in
knot.
The
universality
this
building
was
verified
1,5-naphthyl-containing
ligand.
Quantitative
conversion
simple
macrocycle
species
accomplished
adjusting
concentrations
monitored
NMR
spectroscopy
electrospray
ionization
mass
spectrometry
(ESI-MS).
Furthermore,
increasing
stiff
π-conjugated
area
unit
afforded
ring,
topology
is
topological
isomer
link.
These
artificial
metalla-links
metalla-knots
were
confirmed
single-crystal
X-ray
diffraction,
ESI-MS.
results
offer
potent
higher-order
MIMs
emphasize
critical
role
that
play
creating
sophisticated
topologies.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(18)
Опубликована: Фев. 7, 2024
Abstract
Although
the
synthesis
of
mechanically
interlocked
molecules
has
been
extensively
researched,
selectively
constructing
homogeneous
linear
[4]catenanes
remains
a
formidable
challenge.
Here,
we
constructed
metalla[4]catenane
in
one‐step
process
through
coordination‐driven
self‐assembly
bidentate
benzothiadiazole
derivative
ligand
and
binuclear
half‐sandwich
rhodium
precursor.
The
formation
metalla[4]catenanes
was
facilitated
by
cooperative
interactions
between
strong
sandwich‐type
π‐π
stacking
non‐classical
hydrogen
bonds
components.
Moreover,
modulating
aromatic
substituents
on
precursor,
two
metalla[2]catenanes
were
obtained.
molecular
structures
these
metallacatenanes
unambiguously
characterized
single‐crystal
X‐ray
diffraction
analysis.
Additionally,
reversible
structural
transformation
metal‐catenanes
corresponding
metallarectangles
could
be
achieved
altering
their
concentration,
as
confirmed
mass
spectrometry
NMR
spectroscopy
studies.
Inorganic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Май 8, 2025
The
self-assembly
of
metallo-supramolecules
has
attracted
considerable
attention
in
recent
decades.
These
discrete
architectures
are
primarily
driven
by
coordination
interactions,
typically
involving
M-N/O
(Werner-type)
or
M-C
(organometallic)
bonding.
However,
the
use
M-π
interactions
for
constructing
these
multinuclear
complexes
remains
largely
unexplored.
In
this
work,
we
report
trinuclear
and
tetranuclear
copper(I)
a
combination
interactions.
Cu(I)-NHC
were
synthesized
from
nido-carborane-supported
N-heterocyclic
carbene
(NHC)
precursors
Cu(I)
ions.
solution,
dynamic
equilibrium
between
species
was
observed,
as
confirmed
variable-temperature
NMR
spectrum.
Van't
Hoff
analysis
revealed
that
is
endothermic
(ΔHeq
=
53.6
kJ
mol-1)
entropically
(ΔSeq
158
J
mol-1
K-1).
solid-state
structures
both
forms
elucidated
through
single-crystal
XRD
analysis.
Density
functional
theory
calculations
showed
Cu-CNHC
bonds
relatively
weak
(∼100
mol-1,
approximately
one-third
strength
typical
bonds).
This
attributed
to
strong
Coulombic
attraction
positively
charged
negatively
nido-carborane
ligands
(M-π
interactions),
which
significantly
reduces
bond
neutral
NHC
moieties
(M-C
bonding).
Chemical Communications,
Год журнала:
2024,
Номер
60(43), С. 5573 - 5585
Опубликована: Янв. 1, 2024
Metal-organic
self-assembly
with
flexible
moieties
is
a
budding
field
of
research
due
to
the
possibility
formation
unique
architectures.
Tetrazole,
characterised
by
four
nitrogen
atoms
in
five-member
ring,
exhibits
immense
potential
as
component.
Tetrazole
offers
coordination
sites
for
binding
metal
centre
nine
distinct
modes,
leading
various
assemblies.
This
review
highlights
different
polymeric
and
discrete
tetrazole-based
assemblies
their
functions.
The
meticulous
manipulation
stoichiometry,
ligands,
ions
required
constructing
has
also
been
discussed.
applications
these
architectures
separation,
catalysis
detection
have
accentuated.
latter
section
consolidates
cage
composites,
highlighting
cell
imaging
photocatalytic
applications.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
unknown
Опубликована: Авг. 20, 2024
In
this
work,
a
noncoplanar
terphenyl
served
as
building
block
to
synthesize
novel
3,3'-substituted
bipyridyl
ligand
(L1)
which
further
reacted
with
binuclear
half-sandwich
units
A/B,
giving
rise
two
aesthetic
4
Inorganic Chemistry,
Год журнала:
2024,
Номер
63(32), С. 14924 - 14932
Опубликована: Июнь 19, 2024
Research
on
the
synthesis
of
catenated
cages
has
been
a
growing
field
interest
in
past
few
years.
While
multiple
types
with
different
structures
have
synthesized,
application
such
systems
much
less
explored.
Specifically,
use
separation
industrially
relevant
molecules
that
are
present
coal
tar
not
explored
before.
Herein,
we
demonstrate
newly
synthesized
interlocked
cage
1
[C184H240N76O48Pd6]
(M6L4),
formed
through
self-assembly
ligand
L.HNO3
(tris(4-(1H-imidazole-1-yl)benzylidene)hydrazine-1-carbohydrazonhydrazide)
acceptor
cis-[(tmchda)Pd(NO3)2]
[tmchda
=
±N,N,N′,N′-tetramethylcyclohexane-1,2-diamine]
(M).
The
was
able
to
separate
isomers
(anthracene
and
phenanthrene)
using
simple
solvent
extraction
technique.
Using
same
technique,
more
difficult
structurally
physiochemically
similar
compounds
acenaphthene
acenaphthylene
performed
for
first
time
as
host.
Other
noninterlocked
hexanuclear
Pd6
having
wider
cavity
proved
inefficient
separation,
demonstrating
uniqueness
challenging
separation.
JACS Au,
Год журнала:
2024,
Номер
4(8), С. 3238 - 3247
Опубликована: Авг. 15, 2024
Molecular
hosts
with
functional
cavities
can
emulate
enzymatic
behavior
through
selective
encapsulation
of
substrates,
resulting
in
high
chemo-,
regio-,
and
stereoselective
product
formation.
It
is
still
challenging
to
synthesize
enzyme-mimicking
that
exhibit
a
narrow
substrate
scope
relies
upon
the
recognition
substrates
based
on
molecular
size.
Herein,
we
introduce
Pd
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(8)
Опубликована: Янв. 5, 2024
Abstract
We
report
a
novel
strategy
for
reversible
modulation
of
the
supramolecular
chirality
based
on
guest‐facilitated
heteroleptic
assembly
helical
anionocages.
Two
triple‐stranded
anionocages
including
chiral
cage
1
(A
2
L
3
)
and
crown
ether
functionalized
achiral
were
synthesized
by
anion
coordination
bis‐monourea‐based
ligands
PhPO
2−
.
Both
cages
exhibited
favorable
binding
with
tetraethylammonium
TEA
+
cobaltocenium
Cob
(endo‐guest,
bound
in
cavity).
Additionally,
could
reversibly
release
recapture
guests
through
exo‐guest
potassium
ions
(K
ethers
subsequent
removal
K
[2,2,2]‐cryptand.
The
circular
dichroism
(CD)
spectrum
was
not
significantly
affected
guest
encapsulation
or
mixing
“empty”
However,
presence
both
an
endo‐guest/exo‐guest,
Cotton
effects
reversed
at
391
nm
enhanced
310
nm.
This
observation
attributed
to
formation
that
enabled
effective
transfer
from
ligands.
CD
changes
induced
be
fully
removing
it
Sequential
addition
allowed
least
10
cycles
without
significant
attenuation.
Chemical Science,
Год журнала:
2024,
Номер
15(31), С. 12502 - 12510
Опубликована: Янв. 1, 2024
A
tetradentate
ligand
with
two
different
donor
groups
gave
unsymmetrical
molecular
barrel
UNMB
via
self-assembly.
The
stronger
binding
affinity
of
towards
C
70
over
60
was
used
to
extract
from
a
mixture
/C
in
high
purity.
