3D N-heterocyclic covalent organic frameworks for urea photosynthesis from NH3 and CO2
Nature Communications,
Год журнала:
2025,
Номер
16(1)
Опубликована: Янв. 28, 2025
Abstract
Artificial
photosynthesis
of
urea
from
NH
3
and
CO
2
seems
to
remain
still
essentially
unexplored.
Herein,
three
isomorphic
three-dimensional
covalent
organic
frameworks
with
twofold
interpenetrated
ffc
topology
are
functionalized
by
benzene,
pyrazine,
tetrazine
active
moieties,
respectively.
A
series
experiment
results
disclose
the
gradually
enhanced
conductivity,
light-harvesting
capacity,
photogenerated
carrier
separation
efficiency,
co-adsorption
capacity
towards
in
order
benzene-,
pyrazine-,
tetrazine-containing
framework.
This
turn
endows
framework
superior
photocatalytic
activity
production
yield
523
μmol
g
−1
h
,
40
4
times
higher
than
that
for
benzene-
pyrazine-containing
framework,
respectively,
indicating
heterocyclic
N
microenvironment-dependent
catalytic
performance
these
photocatalysts.
is
further
confirmed
in-situ
spectroscopic
characterization
density
functional
theory
calculations.
work
lays
a
way
sustainable
urea.
Язык: Английский
Self-Assembly and Dynamic Equilibrium of Trinuclear and Tetranuclear Cu(I) Supramolecules Featuring nido-Carborane-Supported N-Heterocyclic Carbene Ligands
Yun-Kang Ren,
Yiwen Li,
Mei-Juan Liang
и другие.
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).
Язык: Английский
A 12-Vertex Metallacarborane of Silver(I)
Inorganic Chemistry,
Год журнала:
2024,
Номер
63(12), С. 5481 - 5486
Опубликована: Март 6, 2024
The
discovery
of
ferrocene
in
1951
was
a
significant
landmark
the
field
organometallic
chemistry,
and
since
then,
numerous
sandwich-
or
half-sandwich
metallic
complexes
have
been
reported.
However,
silver
stands
as
an
intriguing
exception
this
regard,
knowledge
its
bonding
situation
has
remained
undisclosed.
Herein,
unprecedented
12-vertex
metallacarboranes
Ag(I)
(2a
2b)
were
synthesized
through
reaction
sodium
hexamethyldisilazide
(NaHMDS)
with
mixture
nido-C2B9
carborane
anion-supported
N-heterocyclic
carbene
precursors
(1a
1b)
[Ag(PPh3)Cl]4.
X-ray
structural
analysis
resulting
revealed
unique
"slipped"
structure,
which
is
rarity
among
cyclopentadienyl
analogues.
DFT
calculations
provided
insights
into
asymmetric
π-interactions
between
pentagonal
C2B3
face
ion.
Язык: Английский
Palladium-Catalyzed Cross-Coupling Reactions of Carboranes with Alkenes via Selective B–H Bond Activation
Organic Letters,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 17, 2025
A
palladium-catalyzed
Heck-type
cross-coupling
reaction
of
carboranes
with
alkenes
in
1,1,1,3,3,3-hexafluoro-2-propanol
(HFIP)
was
realized.
This
shows
good
B(9)
selectivity
for
m-carboranes
and
is
also
suitable
o-
p-carborane.
Meanwhile,
a
series
mono-,
di-,
trisubstituted
were
compatible
substrates
to
afford
the
alkenylated
products
16–89%
yields.
The
1,2-bis(carboranyl)ethylene
first
synthesized
by
vinyltrimethylsilane
m-carborane.
Further
transformations
C═C
bond
product
examined
hydroboration
oxidation,
hydroboration,
bromination
generate
corresponding
B(9)-functionalized
m-carboranes.
Язык: Английский
A comparative study on nido- and closo-carborane supported zinc-salen catalysts for the ROCOP of epoxides and anhydrides
Dalton Transactions,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
Nido
-C
2
B
9
carborane
anion
supported
Zn–salen
complexes
are
superior
to
closo
-carborane
ones
in
ROCOP
of
epoxides
and
anhydrides.
Язык: Английский
Palladium-Catalyzed Regioselective B(3,4,5,6)–H Tetra-Arylation of o-Carboranes
Inorganic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Май 21, 2025
A
transition-metal-catalyzed
iterative
multiple
cage
B-H
activation
reaction
for
constructing
multifunctionalization
of
o-carboranes
in
one
pot
is
challenging.
Herein,
palladium-catalyzed
regioselective
tetra-arylation
a
wide
range
C(1)-N-aryl-o-carboranyl
amides
with
aryl
iodides
has
been
developed.
variety
B(3,4,5,6)-tetra-arylated
were
synthesized
good-to-excellent
yields.
Moreover,
the
mono-,
di-,
and
triarylated
intermediate
products
isolated,
exact
structures
determined
by
NMR,
high-resolution
mass
spectrometry,
X-ray
analysis,
which
provide
rationale
that
order
introduction
groups
into
o-carborane
B(4)
>
B(5)
B(3)/B(6).
This
protocol
represents
powerful
synthetic
method
polyfunctionalization
derivatives
under
very
mild
simple
conditions,
offers
valuable
reference
design
synthesis
molecular
propellers
based
on
carboranes.
Язык: Английский
9,9′-Bis-o-carboranes: synthesis and exploration of properties
Chemical Communications,
Год журнала:
2023,
Номер
60(5), С. 614 - 617
Опубликована: Дек. 6, 2023
A
highly
efficient
Pd-catalyzed
B(9)-H/B(9)-H
oxidative
dehydrogenation
coupling
of
carboranes
to
synthesize
9,9'-bis-
Язык: Английский
Asymmetric synthesis of metallacarboranes using a traceless chiral auxiliary
Organic Chemistry Frontiers,
Год журнала:
2023,
Номер
10(23), С. 5965 - 5970
Опубликована: Янв. 1, 2023
An
asymmetric
synthesis
of
chiral
metallacarboranes
using
a
traceless
N-tert
butylsulfinamide
auxiliary
is
reported.
Язык: Английский
Nickel(II) and Palladium(II) Complexes with η5:κ1(N)-Coordinated Dicarbollide Ligands Containing Pendant Pyridine Group
International Journal of Molecular Sciences,
Год журнала:
2023,
Номер
24(20), С. 15069 - 15069
Опубликована: Окт. 11, 2023
A
series
of
C-
and
B-substituted
nido-carborane
derivatives
with
a
pendant
pyridyl
group
was
prepared.
The
synthesized
compounds
were
used
as
ligands
in
the
complexation
reactions
bis(triphenylphosphine)nickel(II)
palladium(II)
chlorides
to
give
six
new
metallacomplexes
unusual
η5:κ1(N)-coordination
metal
center.
single
crystal
structures
1-(NC5H4-2′-S)-1,2-C2B10H11,
1-(NC5H4-2′-CH2S)-1,2-C2B10H11,
Cs
[7-(NC5H4-2′-CH2S)-7,8-C2B9H11]
closo-
nido-carboranes
3-Ph3P-3-(4(7)-NC5H4-2′-S)-closo-3,1,2-NiC2B9H10
3-Ph3P-3-(4(7)-NC5H4-2′-CH2S)-closo-3,1,2-NiC2B9H10
metallacarboranes
determined
using
X-ray
diffraction.
Язык: Английский