Phenol[4]arenes: Excellent Macrocyclic Precursors for Constructing Chiral Porous Organic Cages
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 2, 2025
The
development
of
new
chiral
building
blocks
for
constructing
complex
architectures,
such
as
macrocycles
and
cages,
is
both
crucial
challenging.
Although
concave-shaped
calixarenes
have
been
established
versatile
the
synthesis
cage
compounds,
there
are
no
reports
on
cages
constructed
from
calix[4]arene
derivatives.
Herein,
we
present
a
straightforward
effective
method
gram-scale
member
macrocycle
enantiomers,
namely,
phenol[4]arene
(PC[4]A).
As
proof
concept,
functionalized
these
enantiomers
into
tetraformylphenol[4]arene
(PC[4]ACHO)
derivatives
via
Duff
reaction
to
construct
porous
organic
(CPOCs)
using
polyamine
synthons.
Specifically,
employ
two
fluorescent
amine
synthons,
bis(4-aminophenyl)phenylamine
tris(4-aminophenyl)amine,
assemble
with
PC[4]ACHO
resulting
in
[2
+
4]
lantern-shaped
[6
8]
truncated
octahedral
CPOCs,
respectively.
These
structures
unambiguously
characterized
by
single-crystal
X-ray
diffraction
circular
dichroism
(CD)
spectroscopy.
Notably,
CPOCs
exhibit
internal
diameters
approximately
3.1
nm,
cavity
volume
around
5300
Å3,
high
specific
surface
areas
up
1300
m2
g-1
after
desolvation,
making
them
among
largest
reported.
Additionally,
investigations
their
sensing
performance
demonstrate
that
PC[4]A-based
enable
enantioselective
recognition
amino
acids
This
work
strongly
suggests
PC[4]A
can
serve
an
excellent
block
rational
design
materials
practical
applications.
Язык: Английский
A Perspective on Carbon–Carbon Diradical-Mediated Dynamic Covalent Synthesis of Organic Macrocycles and Their Emerging Functions
Crystal Growth & Design,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 15, 2025
A
biological
self-assembly
of
organized
supramolecular
structures
and
functional
materials
has
emerged
as
a
significant
research
focus
in
recent
decades.
Different
strategies
have
been
proposed
successfully
adopted
for
engineering
complex
structures.
Among
others,
substantial
progress
made
using
dynamic
covalent
chemistry
(DCC)
to
generate
with
sophisticated
properties.
This
Perspective
elaborates
on
the
role
carbon–carbon
(C–C)-based
diradical-based
DCC
self-assembly.
It
provides
an
in-depth
discussion
structural
aspects
C–C
bonds
discrete
oligomer
formation
including
dimers,
trimers,
tetramers,
hexameric
Early
sections
survey
critical
factors
contributing
longevity
stability
radical
systems
influences
substitution
diradicals
into
dimers
or
macrocycles.
Significant
attention
given
characteristics
diradical
impact
hydrogen
π–π
interactions
configurations
self-assembled
The
latter
part
this
article
properties
applications
DCC-mediated
primary
objectives
review
are
(i)
present
detailed
analysis
benefits
associated
diradical-mediated
(ii)
investigate
their
Язык: Английский
Chiral Pt(II)–V(V) Bimetallic Cages and Guest-Induced Allosteric Regulation of Catalytic Asymmetric Sulfoxidation
Inorganic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 6, 2025
Flexible
metal–organic
cages
can
provide
confined
active
metal
sites
and
show
promise
in
mimicking
metalloenzymes.
In
this
study,
we
synthesized
two
flexible
chiral
bimetallic
coordination
cages,
[(PEt3)6Pt3(R,R,R-VL)2]6+
its
enantiomer,
through
the
self-assembly
of
platinum(II)
precursors
with
enantiopure
tripodal
vanadium(V)
complexes
bearing
pendant
pyridyl
groups
(VL).
The
guest
binding
camphorsulfonate
anions,
concomitant
changes
cage
conformation.
catalytic
properties
for
oxidizing
thioethers
into
sulfoxides
were
investigated
comparison
a
simple
complex.
While
complex,
either
alone
or
along
camphorsulfonate,
does
not
any
enantioselectivity,
enables
enantioselective
oxidation
even
though
enantiomeric
excess
is
low.
stereoselectivity
significantly
improved
after
introduced
to
cage.
acts
like
an
allosteric
effector
enzymes
modulate
conformation
local
microenvironment
around
site
favor
induction.
This
work
highlights
potentials
leveraging
cage-confined
host–guest
interactions
advancing
supramolecular
asymmetric
catalysis.
Язык: Английский
Beyond symmetric self-assembly and effective molarity: unlocking functional enzyme mimics with robust organic cages
Beilstein Journal of Organic Chemistry,
Год журнала:
2025,
Номер
21, С. 421 - 443
Опубликована: Фев. 24, 2025
The
bespoke
environments
in
enzyme
active
sites
can
selectively
accelerate
chemical
reactions
by
as
much
1019.
Macromolecular
and
supramolecular
chemists
have
been
inspired
to
understand
mimic
these
accelerations
selectivities
for
applications
catalysis
sustainable
synthesis.
Over
the
past
60+
years,
mimicry
strategies
evolved
with
changing
interests,
understanding,
synthetic
advances
but,
ubiquitously,
research
has
focused
on
use
of
a
molecular
"cavity".
activities
different
cavities
vary
subset
features
available
particular
cavity
type.
Unsurprisingly,
without
access
mimics
able
encompass
more/all
functional
sites,
examples
cavity-catalyzed
processes
demonstrating
enzyme-like
rate
remain
rare.
This
perspective
will
briefly
highlight
some
key
traditional
catalysis,
type,
order
contextualize
recent
development
robust
organic
cage
catalysts,
which
exploit
stability,
functionality,
reduced
symmetry
enable
promising
catalytic
modes.
Язык: Английский
Metal-free porphyrin porous organic cage for efficient iodine capture
Chemical Engineering Journal,
Год журнала:
2025,
Номер
unknown, С. 161326 - 161326
Опубликована: Март 1, 2025
Язык: Английский
Synthesis of a Pd2L4 Hydrazone Molecular Cage Through Multiple Reaction Pathways
International Journal of Molecular Sciences,
Год журнала:
2024,
Номер
25(22), С. 11861 - 11861
Опубликована: Ноя. 5, 2024
Molecular
cages
are
preorganized
molecules
with
a
central
cavity,
typically
formed
through
the
reaction
of
their
building
blocks
chemical
bonds.
This
requires,
in
most
cases,
forming
and
breaking
reversible
bonds
during
cage
formation
pathway
for
error
correction
to
drive
product.
In
this
work,
we
focus
on
both
Pd-ligand
hydrazone
implemented
structure
Pd
Язык: Английский