Molecular
nonequilibrium
systems
hold
great
promises
for
the
nanotechnology
of
future.
Yet,
their
development
is
slowed
by
absence
an
informative
representation.
Indeed,
while
potential
energy
surfaces
comprise
in
principle
all
information,
they
hide
dynamic
interplay
multiple
reaction
pathways
underlying
systems,
i.e.,
degree
kinetic
asymmetry.
To
offer
insightful
visual
representation
asymmetry,
we
extended
approach
pertaining
to
catalytic
networks,
span
model,
focusing
on
system
dynamics
-
rather
than
thermodynamics.
Our
encompasses
both
chemically
and
photochemically
driven
ranging
from
unimolecular
motors
simple
self-assembly
schemes.
The
obtained
diagrams
give
immediate
access
information
needed
guide
experiments,
such
as
states'
population,
rate
machine
operation,
maximum
work
output,
effects
design
changes.
proposed
barrier
a
unifying
graphical
tool
disparate
phenomena.
Journal of the American Chemical Society,
Год журнала:
2021,
Номер
144(2), С. 872 - 882
Опубликована: Дек. 21, 2021
Mechanically
interlocked
networks
(MINs)
have
emerged
as
an
encouraging
platform
for
the
development
of
mechanically
robust
yet
adaptive
materials.
However,
difficulty
in
reversibly
breaking
mechanical
bonds
poses
a
real
challenge
to
MINs
customizable
and
sustainable
Herein,
we
couple
vitrimer
chemistry
with
structures
generate
new
class
MINs─referred
vitrimers
(MIVs)─to
address
challenge.
Specifically,
prepared
acetoacetate-decorated
[2]rotaxane
that
undergoes
catalyst-free
condensation
reaction
two
commercially
available
multiamine
monomers
furnish
MIVs.
Compared
control
whose
wheels
are
nonslidable
under
applied
force,
our
MIVs
slidable
motifs
showcase
enhanced
performance
including
Young's
modulus
(18.5
±
0.9
vs
1.0
0.1
MPa),
toughness
(3.7
MJ/m3),
damping
capacity
(98%
72%).
The
structural
basis
behind
unique
property
profiles
is
demonstrated
be
force-induced
host-guest
dissociation
consequential
intramolecular
sliding
along
axles.
peculiar
behaviors
represent
consecutive
energy
dissipation
mechanism,
which
provides
complement
other
pathways
mainly
depend
on
sacrificial
bonds.
Moreover,
by
virtue
vinylogous
urethanes,
impart
reprocessability
chemical
recyclability
MINs,
thereby
empowering
reconfiguration
without
Finally,
it
disclosed
motions
[2]rotaxanes
could
accelerate
dynamic
exchange
urethane
via
loosening
network,
suggestive
synergistic
effect
between
dual
entities.
Science,
Год журнала:
2021,
Номер
374(6572), С. 1215 - 1221
Опубликована: Окт. 22, 2021
Over
the
past
century,
adsorption
has
been
investigated
extensively
in
equilibrium
systems,
with
a
focus
on
van
der
Waals
interactions
associated
physisorption
and
electronic
case
of
chemisorption.
In
this
study,
we
demonstrate
mechanisorption,
which
results
from
nonequilibrium
pumping
to
form
mechanical
bonds
between
adsorbent
adsorbate.
This
active
mode
realized
surfaces
metal-organic
frameworks
grafted
arrays
molecular
pumps.
Adsorbates
are
transported
one
well-defined
compartment,
bulk,
another
interface,
thereby
creating
large
potential
gradients
chemical
capacitors
wherein
energy
is
stored
metastable
states.
Mechanisorption
extends,
fundamental
manner,
scope
phenomena
offers
transformative
approach
control
chemistry
at
interfaces.
Nature,
Год журнала:
2023,
Номер
613(7943), С. 280 - 286
Опубликована: Янв. 11, 2023
Macroscopic
electric
motors
continue
to
have
a
large
impact
on
almost
every
aspect
of
modern
society.
Consequently,
the
effort
towards
developing
molecular
Nature Communications,
Год журнала:
2023,
Номер
14(1)
Опубликована: Июнь 1, 2023
Cu-based
nanocatalysts
are
the
cornerstone
of
various
industrial
catalytic
processes.
Synergistically
strengthening
stability
and
activity
is
an
ongoing
challenge.
Herein,
high-entropy
principle
applied
to
modify
structure
nanocatalysts,
a
PVP
templated
method
invented
for
generally
synthesizing
six-eleven
dissimilar
elements
as
two-dimensional
(2D)
materials.
Taking
2D
Cu2Zn1Al0.5Ce5Zr0.5Ox
example,
not
only
enhances
sintering
resistance
from
400
°C
800
but
also
improves
its
CO2
hydrogenation
pure
CO
production
rate
417.2
mmol
g-1
h-1
at
500
°C,
4
times
higher
than
that
reported
advanced
catalysts.
When
photothermal
hydrogenation,
it
exhibits
record
photochemical
energy
conversion
efficiency
36.2%,
with
generation
248.5
571
L
yield
under
ambient
sunlight
irradiation.
The
materials
provide
new
route
simultaneously
achieve
activity,
greatly
expanding
application
boundaries
catalysis.
Nature Communications,
Год журнала:
2022,
Номер
13(1)
Опубликована: Март 16, 2022
Molecular
necklaces
have
attracted
much
research
attention
due
to
their
unique
topological
structures.
Although
numerous
molecular
with
exquisite
structures
been
constructed,
it
remains
a
major
challenge
exploit
the
functions
and
applications
associated
fascinating
architectural
dynamic
characteristics.
Herein,
we
report
class
of
mechanically
interlocked
networks
(MINs)
cross-linked
by
necklace,
in
which
multiple
crown
ethers
are
threaded
on
hexagonal
metallacyclic
framework
furnish
cross-linker
delicate
The
necklace
possesses
peculiar
advantages:
multivalent
interactions
rigid
metallacycle
guarantee
robust
features
MINs
while
motion
dissociation
bring
notable
mechanical
adaptivity.
Moreover,
could
respond
stimuli
K+
Br-,
lead
dethreading
ether
even
complete
decomposition
respectively,
showing
abundant
active
properties.
These
findings
demonstrate
untapped
potential
as
cross-linkers
open
door
extend
advanced
intelligent
supramolecular
materials.
