Organic Chemistry Frontiers,
Journal Year:
2023,
Volume and Issue:
10(12), P. 3074 - 3079
Published: Jan. 1, 2023
This
frontier
article
summarizes
the
recent
developments
in
base
metal-catalyzed
regioselective
cage
B–H
functionalization
of
carboranes
and
discusses
related
challenging
issues.
Inorganic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 12, 2025
Coordination
cages
with
specific
properties
and
functionalities
are
utilized
as
reaction
vessels
for
the
desired
chemical
transformation
of
substrates.
The
symmetry
inherent
cavity
coordination
can
influence
host–guest
interactions
outcome
in
their
confined
space.
However,
impact
cage
shape
on
different
transformations
remains
unclear.
In
this
chapter,
we
report
chemo-selective
anthracene
derivative
using
three
geometrically
distinct
Pd6
(CC2,
CC3,
CC4).
Photoirradiation
9-bromoanthracene
(G3)
distorted
double-square
(CC2)
yields
anthracene-9,10-dione,
while
known
(CC3)
forms
a
[4
+
4]
cycloaddition
product.
same
bowl-shaped
(CC4)
resulted
oxidized
Through
combination
experimental
computational
studies,
demonstrate
that
size
significantly
pathways
encapsulated
derivative,
leading
to
chemo-selectivity.
Furthermore,
observe
encapsulation
cavities
(CC2
CC4)
leads
significant
enhancement
rate
photooxidation
G3.
This
work
underscores
versatility
water-soluble
synthetic
chemistry,
offering
interesting
avenues
transformation.
Inorganic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: May 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).
Inorganic Chemistry,
Journal Year:
2022,
Volume and Issue:
62(2), P. 885 - 892
Published: Dec. 30, 2022
A
facile
halogenation
method
for
highly
selective
synthesis
of
9-X-o-carboranes,
9,12-X2-o-carboranes,
9-X-12-X'-o-carboranes,
9-X-m-carboranes,
9,10-X2-m-carboranes,
and
9-X-10-X'-m-carboranes
(X,
X'
=
Cl,
Br,
I)
has
been
developed
on
the
basis
our
previous
work.
The
success
this
transformation
relies
usage
trifluoromethanesulfonic
acid
(HOTf),
easily
available
strong
Brønsted
acid.
addition
HOTf
greatly
increases
electrophilicity
N-haloamides
through
hydrogen
bonding
interaction,
resulting
in
low
loading
N-haloamides,
short
reaction
time,
mild
conditions.
Additionally,
solvent
1,1,1,3,3,3-hexafluoro-2-propanol
(HFIP)
is
also
essential
to
further
increase
acidity
HOTf.
Angewandte Chemie,
Journal Year:
2023,
Volume and Issue:
135(20)
Published: March 17, 2023
Abstract
Intricately
interwoven
topologies
are
continually
being
synthesized
and
ultimately
equally
versatile
significant
at
the
nanoscale
level;
however,
reports
concerning
ravel
structures,
which
highly
entwined
new
topological
species,
extremely
rare
fraught
with
tremendous
synthesis
challenges.
To
solve
problem,
a
tetrapodontic
pyridine
ligand
L1
two
types
of
olefinic
bond
units
Cp*M‐based
building
blocks
(
E1
,
M=Rh;
E2
M=Ir)
featuring
large
conjugated
planes
was
prepared
to
perform
self‐assembly.
Two
unprecedented
[5+10]
icosanuclear
molecular
4‐ravels
containing
four
crossings
were
obtained
by
parallel‐displaced
π⋅⋅⋅π
interactions
in
single‐step
strategy.
Remarkably,
reversible
structural
transformations
between
4‐ravel
corresponding
metallocage
could
be
realized
concentration
changes
solvent‐
guest‐induced
effects.
X‐ray
crystallographic
data
NMR
spectroscopy
provide
full
confirmation
these
phenomena.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(28), P. 15538 - 15546
Published: July 6, 2023
Metallacarboranes
have
attracted
significant
attention
due
to
their
unique
properties.
Considerable
efforts
been
made
on
the
reactions
around
metal
centers
or
ion
itself,
while
transformations
of
functional
groups
metallacarboranes
much
less
explored.
We
presented
here
formation
imidazolium-functionalized
nickelacarboranes
(2),
subsequent
conversion
nickelacarborane-supported
N-heterocyclic
carbenoids
(NHCs,
3),
and
reactivities
3
toward
Au(PPh3)Cl
Se
powder,
which
resulted
in
bis-gold
carbene
complexes
(4)
NHC
selenium
adducts
(5).
Cyclic
voltammetry
4
shows
two
reversible
peaks,
corresponding
interconversion
NiII
↔
NiIII
NiIV.
Theoretical
calculations
demonstrated
relatively
high-lying
lone-pair
orbitals,
weak
B-H···H-C
interactions
between
BH
units
methyl
group,
B-H···π
vacant
p-orbital
carbene.
Advanced Optical Materials,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Oct. 15, 2024
Abstract
Photothermal
modulated
excited
conformations
in
traditional
optoelectronic
materials
have
been
extensively
investigated
for
the
manipulation
of
emissive
properties.
However,
photoinduced
molecular
synergetic
conformational
changes,
which
are
promising
controlling
intramolecular
energy
transfer
modes
through
orbital
breaking,
never
explored.
Herein,
a
novel
o
‐carborane
dyad
composed
carbazole
units
as
electron
donors
and
triazine
derivatives
acceptors
is
demonstrated
to
achieve
conformation‐dependent
emissions
abundant
via
changes.
Notably,
resulting
exhibited
multiple
changes
that
induced
different
involved
“through
space”
bond.”
Exactly,
spin
from
singlet
triplet
state
took
flip
accompanied
by
orbitals
π–π
space
charge
style
π
σ
bond
mode.
The
circularly
polarized
luminescence
(CPL)
properties
systematically
investigated,
exhibiting
intense
CPL
with
large
g
lum
values.
These
results
provide
perspectives
elucidating
complicated
emission
aggregated
states,
well
unique
on
relationship
between
conformations,
modes,
breaking.
Angewandte Chemie,
Journal Year:
2023,
Volume and Issue:
135(28)
Published: May 11, 2023
Abstract
Construction
of
metal–organic
cages
with
unique
architecture
and
guest
binding
abilities
is
highly
desirable.
Herein,
we
report
the
synthesis
a
distorted
trigonal
cage
(
1
)
from
twisted
tetratopic
ligand
L
Pd
II
acceptor.
Surprisingly,
exhibited
complete
structural
reorganization
its
building
units
in
presence
C
70
60
to
form
guest‐encapsulated
tetragonal
cages,
(C
2
@
,
respectively.
These
guest‐bound
were
found
be
potential
O
generators,
former
effectively
catalyzing
two
different
varieties
‐mediated
oxidation
reactions.
Organic Chemistry Frontiers,
Journal Year:
2023,
Volume and Issue:
10(13), P. 3293 - 3299
Published: Jan. 1, 2023
Two
o
-carborane-based
π-conjugated
macrocycles
were
synthesized.
Single-crystal
structures
revealed
their
micropore
characteristics.
These
exhibit
aggregation-induced
emission
and
selective
identification.
