Angewandte Chemie,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 2, 2024
Abstract
Metal–organic
frameworks
(MOFs)
have
been
widely
studied
due
to
their
versatile
applications
and
easily
tunable
structures.
However,
heteroatom‐metal
coordination
dominates
the
MOFs
community,
rational
synthesis
of
carbon–metal
coordination‐based
remains
a
significant
challenge.
Herein,
two‐dimensional
(2D)
based
on
silver–carbon
linkages
are
synthesized
through
between
silver(I)
salt
isocyanide‐based
monomers
at
ambient
condition.
The
as‐synthesized
2D
possess
well‐defined
crystalline
structures
staggered
AB
stacking
mode.
Most
interestingly,
these
MOFs,
without
π–π
layers,
exhibit
narrow
band
gaps
down
1.42
eV.
As
electrochemical
catalysts
for
converting
CO
2
CO,
such
demonstrate
Faradaic
efficiency
over
92
%.
Surprisingly,
reduction
catalyzed
by
indicates
favorable
adsorption
*COOH
active
carbon
sites
isocyanide
groups
rather
than
silver
sites.
This
is
attributed
critical
σ
donor
role
isocyanides
corresponding
ligand‐to‐metal
charge–transfer
effect.
work
not
only
paves
way
toward
new
family
metal–isocyanide
but
also
offers
rare
platform
understanding
electrocatalysis
processes
strongly
polarized
species.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(15), С. 10418 - 10431
Опубликована: Апрель 8, 2024
Light-triggered
dissociation
of
ligands
forms
the
basis
for
many
compounds
interest
photoactivated
chemotherapy
(PACT),
in
which
medicinally
active
substances
are
released
or
"uncaged"
from
metal
complexes
upon
illumination.
Photoinduced
ligand
is
usually
irreversible,
and
recent
studies
performed
context
PACT
focused
on
ruthenium(II)
polypyridines
related
heavy
complexes.
Herein,
we
report
a
first-row
transition
complex,
photoinduced
spontaneous
recoordination
unit
occurs.
Two
scorpionate-type
tridentate
chelates
provide
an
overall
six-coordinate
arylisocyanide
environment
chromium(0).
Photoexcitation
causes
decoordination
one
these
six
ligating
units
coordination
solvent
molecule,
at
least
tetrahydrofuran
1,4-dioxane
solvents,
but
far
less
toluene,
below
detection
limit
cyclohexane.
Transient
UV-vis
absorption
spectroscopy
quantum
chemical
simulations
point
to
directly
excited
metal-to-ligand
charge-transfer
state.
Owing
chelate
design
substitution
lability
metal,
photodissociated
can
occur
spontaneously
millisecond
time
scale.
This
work
provides
insight
into
possible
self-healing
mechanisms
counteracting
unwanted
photodegradation
processes
seems
furthermore
relevant
contexts
photoswitching
(photo)chemical
information
storage.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 27, 2025
Luminescence
and
photochemistry
involve
electronically
excited
states
that
are
inherently
unstable
therefore
spontaneously
decay
to
electronic
ground
states,
in
most
cases
by
nonradiative
energy
release
generates
heat.
This
dissipation
can
occur
on
a
time
scale
of
100
fs
(∼10–13
s)
usually
needs
be
slowed
down
at
least
the
nanosecond
(∼10–9
for
luminescence
intermolecular
occur.
is
challenging
task
with
many
different
factors
consider.
An
alternative
emerging
strategy
target
dissociative
lead
metal–ligand
bond
homolysis
subnanosecond
access
synthetically
useful
radicals.
Based
thorough
review
recent
advances
field,
this
article
aims
provide
concise
guide
obtaining
luminescent
photochemically
coordination
compounds
d-block
elements.
We
hope
encourage
"photo-motivated"
chemists
who
have
been
reluctant
apply
their
synthetic
other
knowledge
photophysics
photochemistry,
we
intend
stimulate
new
approaches
control
state
behavior.
Advanced Optical Materials,
Год журнала:
2025,
Номер
unknown
Опубликована: Май 15, 2025
Abstract
Luminescent
switches
with
multiple
optical
outputs
are
essential
for
meeting
the
growing
demand
high‐security
encryption.
Herein,
symmetric
and
chiral
molecules
designed
synthesized
by
integrating
luminescent
planar
Pt(II)
moieties
into
SS
/
RR
‐trans‐1,2‐cyclohexane
diamine
scaffolds.
This
approach
enables
correlation
of
structures,
assemblies,
optical/chiroptical
properties
these
materials,
which
exhibit
spacer‐dependent
chiroptical
behavior.
The
more
rigid
foldamer
shows
unusual
switching
from
monomer
to
intramolecular
excimers
corresponding
circular
dichroism
circularly
polarized
luminescence
increasing
temperature,
differing
significantly
conventional
chromophores.
Based
on
its
reversible
sensitive
multicolor
phosphorescence
characteristics,
molecular
is
employed
create
a
stepwise
anticounterfeit
ink,
advancing
anti‐counterfeiting
technology.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 2, 2024
Metal-organic
frameworks
(MOFs)
have
been
widely
studied
due
to
their
versatile
applications
and
easily
tunable
structures.
However,
heteroatom-metal
coordination
dominates
the
MOFs
community,
rational
synthesis
of
carbon-metal
coordination-based
remains
a
significant
challenge.
Herein,
two-dimensional
(2D)
based
on
silver-carbon
linkages
are
synthesized
through
between
silver(I)
salt
isocyanide-based
monomers
at
ambient
condition.
The
as-synthesized
2D
possess
well-defined
crystalline
structures
staggered
AB
stacking
mode.
Most
interestingly,
these
MOFs,
without
π-π
layers,
exhibit
narrow
band
gaps
down
1.42
eV.
As
electrochemical
catalysts
for
converting
CO
Inorganic Chemistry,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 16, 2024
There
is
growing
demand
for
the
utilization
of
first-row
transition
metal
complexes
in
light-driven
processes
instead
their
conventional
noble
counterparts
due
to
greater
sustainability
complexes.
However,
major
drawback
ultrafast
lifetime
electronic
excited
states
these
complexes,
particularly
those
d
Chemical Communications,
Год журнала:
2024,
Номер
60(70), С. 9360 - 9363
Опубликована: Янв. 1, 2024
A
photo-controlled
optical
molecular
switch
has
been
achieved.
Apparent
and
emissive
color
changes
under
visible
light
irradiation
temperature
stimulation
have
achieved
used
to
develop
anti-counterfeiting
materials.
Inorganic Chemistry,
Год журнала:
2024,
Номер
63(34), С. 15829 - 15840
Опубликована: Авг. 12, 2024
Three
homoleptic
Al(III)
complexes
(Al1–Al3)
with
different
degrees
of
methylation
at
the
2-pyridylpyrrolide
ligand
were
systematically
tested
for
their
function
as
photosensitizers
(PS)
in
two
types
energy
transfer
reactions.
First,
generation
reactive
singlet
oxygen
(1O2),
and
second,
isomerization
(E)-
to
(Z)-stilbene.
1O2
was
directly
evidenced
by
its
characteristic
NIR
emission
around
1276
nm
indirectly
reaction
an
organic
substrate
[e.g.
2,5-diphenylfuran
(DPF)]
using
situ
UV/vis
spectroscopy.
In
a
previous
study,
presence
additional
methyl
groups
found
be
beneficial
photocatalytic
reduction
CO2
CO,
but
here
Al1
without
any
exhibits
superior
performance.
To
rationalize
this
behavior,
combination
photophysical
experiments
(absorption,
excited
state
lifetimes)
together
photostability
measurements
scalar-relativistic
time-dependent
density
functional
theory
calculations
applied.
As
result,
exhibited
highest
quantum
yield
(64%),
longest
lifetime
(8.7
ns)
best
under
conditions
required
reactions
(e.g.
aerated
chloroform).
Moreover,
provided
rate
constant
(0.043
min–1)
oxygenation
DPF,
outperforming
even
noble
metal-based
competitors
such
[Ru(bpy)3]2+.
Finally,
enabled
long-term
test
(7
h),
which
successfully
recycled
seven
times,
underlining
high
potential
new
class
earth-abundant
PSs.
