Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(24), P. 9274 - 9280
Published: Jan. 1, 2024
Broadening
carborane
applications
has
consistently
been
the
goal
of
chemists
in
this
field.
Herein,
compared
to
alkyl
or
aryl
groups,
a
cage
demonstrates
an
advantage
stabilizing
unique
bonding
interaction:
M⋯C–H
interaction.
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.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(14)
Published: Feb. 2, 2024
Abstract
The
development
of
novel
materials
for
highly
efficient
and
selective
photocatalysis
is
crucial
their
practical
applications.
Herein,
we
employ
the
host‐guest
chemistry
porphyrin‐based
metallacages
to
regulate
generation
reactive
oxygen
species
further
use
them
photocatalytic
oxidation
benzyl
alcohols.
Upon
irradiation,
sole
metallacage
(
6
)
can
generate
singlet
1
O
2
effectively
via
excited
energy
transfer,
while
its
complex
with
C
70
⊃C
opens
a
pathway
electron
transfer
promote
formation
superoxide
anion
(O
⋅
−
),
producing
both
.
addition
4,4′‐bipyridine
(BPY)
forms
more
stable
⊃BPY)
coordination
Zn‐porphyrin
faces
BPY,
which
drives
fullerenes
out
cavities
restores
ability
generation.
Therefore,
alcohols
are
oxidized
into
aldehydes
upon
irradiation
in
presence
or
⊃BPY,
they
benzoic
acids
when
employed
as
photosensitizing
agent.
This
study
demonstrates
strategy
that
utilizes
photooxidation
reactions,
could
utilization
related
complexes
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
63(4)
Published: Nov. 15, 2023
Abstract
The
development
of
multimode
photopatterning
systems
based
on
supramolecular
coordination
complexes
(SCCs)
is
considerably
attractive
in
chemistry
and
materials
science,
because
SCCs
can
serve
as
promising
platforms
for
the
incorporation
multiple
functional
building
blocks.
Herein,
we
report
a
light‐responsive
liquid‐crystalline
metallacycle
that
constructed
by
coordination‐driven
self‐assembly.
By
exploiting
its
fascinating
liquid
crystal
features,
bright
emission
properties,
facile
photocyclization
capability,
unique
system
with
spatially‐controlled
fluorescence‐resonance
energy
transfer
(FRET)
built
through
introduction
photochromic
spiropyran
derivative,
which
led
to
realization
first
example
orthogonal
three‐modes,
namely
holography,
fluorescence,
photochromism.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(36), P. 19440 - 19457
Published: Aug. 29, 2023
The
utilization
of
carboranes
in
supramolecular
chemistry
has
attracted
considerable
attention.
unique
spatial
configuration
and
weak
interaction
forces
can
help
to
explore
the
properties
complexes,
particularly
via
host–guest
chemistry.
Additionally,
certain
difficulties
encountered
carborane
development─such
as
controlled
B–H
bond
activation─can
be
overcome
by
judiciously
selecting
metal
centers
their
adjacent
ligands.
However,
few
studies
are
being
conducted
this
nascent
research
area.
With
advances
field,
novel
carborane-based
complexes
will
likely
prepared,
structurally
characterized,
intrinsically
investigated.
To
expedite
these
efforts,
we
present
major
findings
from
recent
studies,
including
π–π
interactions,
associations,
steric
effects,
which
have
been
leveraged
implement
a
regioselective
process
for
activating
B(2,9)–,
B(2,8)–,
B(2,7)–H
bonds
para-carboranes
B(4,7)–H
ortho-carboranes.
Future
should
clarify
interactions
potential
enhancing
utility
complexes.
Although
exhibit
several
(such
dihydrogen-bond
[Bδ+–Hδ−···Hδ+–Cδ−],
Bδ+–Hδ−···M+,
Bδ+–Hδ−···π
interactions),
manner
they
utilized
remains
unclear.
Supramolecular
those
based
on
chemistry,
platform
demonstrating
applications
interactions.
Owing
importance
alkane
separation,
related
recognition
separation
isomers
primarily
summarized.
Advances
certainly
lead
more
possibilities
Inorganic Chemistry,
Journal Year:
2023,
Volume and Issue:
62(32), P. 12989 - 13000
Published: Aug. 2, 2023
Metal–organic
frameworks
(MOFs)
have
been
recognized
as
one
of
the
most
promising
porous
materials
and
offer
great
opportunities
for
rational
design
new
catalytic
solids
having
structural
diversity
functional
tunability.
Despite
numerous
inherent
merits,
their
chemical
environment
instability
limits
practical
usage
demands
further
exploration.
Herein,
by
employing
mixed-ligand
approach,
we
designed
developed
a
robust
3D
Co-MOF,
[Co2(μ2-O)(TDC)2(L)(H2O)2]·2DMF
(H2TDC
=
2,5-thiophenedicarboxylic
acid,
L
3,3′-azobispyridine),
IITKGP-50
(IITKGP
stands
Indian
Institute
Technology
Kharagpur),
which
exhibited
excellent
framework
robustness
not
only
in
water
but
also
wide
range
aqueous
pH
solutions
(pH
2–12).
Taking
advantage
superior
presence
high-density
open
metal
sites,
was
explored
catalyzing
two-component
Knoevenagel
condensation
reaction
three-component
Strecker
reactions.
Moreover,
to
verify
size
selectivity
IITKGP-50,
smaller
bulkier
substrates
comparison
with
MOF's
pore
cavity
(8.1
×
5.6
Å2)
were
employed,
relatively
lesser
conversions
sterically
aldehyde
derivatives
confirmed
that
cycle
occurs
inside
cavity.
The
easy
scalability,
lower
catalyst
loading
compared
benchmark
MOFs,
magnificent
conversion
rate
over
substrates,
recyclability
without
significant
performance
loss
made
heterogeneous
candidate.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(40)
Published: Aug. 19, 2023
Abstract
Multicomponent
metallacages
can
integrate
the
functions
of
their
different
building
blocks
to
achieve
synergetic
effects
for
advanced
applications.
Herein,
based
on
metal‐coordination‐driven
self‐assembly,
we
report
preparation
a
series
isoreticular
tetraphenylethylene‐based
metallacages,
which
are
well
characterized
by
multinuclear
NMR,
ESI‐TOF‐MS
and
single‐crystal
X‐ray
diffraction
techniques.
The
suitable
integration
photosensitizing
tetraphenylethylene
units
as
faces
Re
catalytic
complexes
pillars
into
single
metallacage
offers
high
photocatalytic
hydrogen
production
rate
1707
μmol
g
−1
h
,
is
one
highest
values
among
reported
metallacages.
Femtosecond
transient
absorption
DFT
calculations
reveal
that
serve
platform
precise
organized
arrangement
two
blocks,
enabling
efficient
directional
electron
transfer
highly
performance.
This
study
provides
general
strategy
multifunctional
ligands
certain
improve
efficiency
production,
will
guide
future
design
towards
photocatalysis.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(22), P. 15301 - 15308
Published: May 24, 2024
Designing
supramolecular
architectures
with
uncommon
geometries
has
always
been
a
key
goal
in
the
field
of
metal–ligand
coordination-driven
self-assembly.
It
acquires
added
significance
if
functional
building
units
are
employed
constructing
such
for
fruitful
applications.
In
this
report,
we
address
both
these
aspects
by
developing
water-soluble
Pd16L8
coordination
cage
1
an
unusual
square
orthobicupola
geometry,
which
was
used
selective
aerobic
oxidation
aryl
sulfides.
Self-assembly
benzothiadiazole-based
tetra-pyridyl
donor
L
ditopic
cis-[(tmeda)Pd(NO3)2]
acceptor
[tmeda
=
N,N,N′,N′-tetramethylethane-1,2-diamine]
produced
1,
and
geometry
determined
single-crystal
X-ray
diffraction
study.
Unlike
typically
observed
tri-
or
tetrafacial
barrel,
present
assembly
features
distinctive
structural
topology
is
unique
example
molecular
architecture
geometry.
Efficient
sulfides
to
sulfoxides
important
challenge
as
conventional
generally
leads
formation
sulfoxide
along
toxic
sulfone.
Cage
designed
ligand
containing
benzothiadiazole
moiety,
demonstrates
ability
photogenerate
reactive
oxygen
species
(ROS)
water,
thus
enabling
it
serve
potential
photocatalyst.
The
showed
excellent
catalytic
efficiency
highly
conversion
alkyl
their
corresponding
sulfoxides,
therefore
without
sulfones
other
byproducts,
under
visible
light
aqueous
medium.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(23), P. 15787 - 15795
Published: May 13, 2024
The
encapsulation
of
different
guest
molecules
by
their
recognition
domains
proteins
leads
to
selective
binding,
catalysis,
and
transportation.
Synthetic
hosts
capable
selectively
binding
guests
in
cavities
mimic
the
function
are
highly
desirable
but
challenging.
Here,
we
report
three
ladder-shaped,
triple-cavity
metallacages
prepared
multicomponent
coordination-driven
self-assembly.
Interestingly,
porphyrin-based
metallacage
is
heteroleptic
fullerenes
(C60
or
C70)
coronene
using
its
cavities,
allowing
distinct
allosteric
upon
addition
C60
C70.
Owing
affinities
one
molecule
central
cavity
two
units
side
while
encapsulating
C70
cavity.
rational
design
multicavity
assemblies
that
enable
will
guide
further
advanced
supramolecular
constructs
with
tunable
properties.
Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: May 4, 2024
Abstract
Coordination
cages
have
been
widely
reported
to
bind
a
variety
of
guests,
which
are
useful
for
chemical
separation.
Although
the
use
in
solid
state
benefits
recycling,
flexibility,
dynamicity,
and
metal-ligand
bond
reversibility
solid-state
poor,
preventing
efficient
guest
encapsulation.
Here
we
report
type
coordination
cage-integrated
materials
that
can
be
swelled
into
gel
water.
The
material
is
prepared
through
incorporation
an
anionic
Fe
II
4
L
6
cage
as
counterion
cationic
poly(ionic
liquid)
(MOC@PIL).
immobilized
within
MOC@PILs
found
greatly
affect
swelling
ability
thus
mechanical
properties.
Importantly,
upon
swelling,
uptake
water
provides
ideal
microenvironment
gels
dynamically
move
flex
leads
excellent
solution-level
binding
performances.
This
concept
has
enabled
adsorbents
removal
pollutants
from
purification
toluene
cyclohexane.
regenerated
deswelling
strategy
along
with
recycling
extracted
guests.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
147(9), P. 7325 - 7335
Published: Feb. 18, 2025
Helicates
are
a
defining
element
of
DNAs
and
proteins,
with
functions
that
critical
to
variety
biological
processes.
Cyclodextrins
promising
candidates
for
forging
multiple-stranded
helicates
well-defined
helicity,
but
lack
available
tools
has
precluded
the
construction
artificial
helical
nanochannels
controllable
geometry
helicity
from
these
widely
chiral
building
blocks.
Herein,
we
disclose
family
Ag6L2
can
be
readily
assembled
α-cyclodextrin-derived
ligands
through
coordination
between
pyridinyl
groups
Ag+
cations.
We
discovered
exhibit
either
an
M
or
P
when
cations
adopt
tetrahedral
while
losing
most
their
linearly
coordinated.
Both
precisely
controlled
by
simply
changing
number
methyl
at
ortho
positions
ligands.
The
tetracoordinated
interconnect
into
infinite
two-dimensional
coordinative
network
characterized
hexagonal
tessellation.
Theoretical
calculations,
which
reveal
lower
energies
conformations
observed
in
crystals
compared
those
inverted
counterparts,
support
experimental
results.