Inorganic Chemistry,
Год журнала:
2024,
Номер
64(1), С. 268 - 274
Опубликована: Дек. 26, 2024
Improved
methods
for
the
synthesis
of
B10H14
and
a
series
N-heterocycle-coordinated
B9H13
complexes
(N-Het·B9H13)
have
been
developed
with
readily
obtained
KB11H14
as
starting
material.
Oxidation
could
provide
in
over
90%
yield.
Then,
N-Het·B9H13
were
prepared
from
as-synthesized
through
situ
multistep
reactions
by
reacting
NaH,
N-heterocycles,
dilute
hydrochloric
acid.
Among
these
complexes,
4-(triphenylvinyl)pyridine-coordinated
(1k)
exhibits
significant
aggregation-induced
emission
(AIE)
effect
THF/H2O
mixed
solution,
8-aminoisoquinoline-coordinated
(2p)
positive
solvatochromism
phenomenon.
These
improved
new
approaches
to
synthesizing
potential
applications
luminescent
materials.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(6), С. 3577 - 3587
Опубликована: Фев. 6, 2023
Aromatic
polycyclic
systems
have
been
extensively
utilized
as
structural
subunits
for
the
preparation
of
various
functional
molecules.
Currently,
aromatics-based
are
predominantly
generated
from
extension
two-dimensional
(2D)
aromatic
rings.
In
contrast,
compounds
based
on
three-dimensional
(3D)
aromatics
such
boron
clusters
less
studied.
Here,
we
report
three
types
cluster-cored
tricyclic
molecular
systems,
which
constructed
a
2D
ring,
3D
nido-carborane,
and
an
alkyne.
These
new
can
be
facilely
accessed
by
Pd-catalyzed
B-H
activation
subsequent
cascade
heteroannulation
carborane
pyridine
with
alkyne
in
isolated
yield
up
to
85%
under
mild
conditions
without
any
additives.
Computational
results
indicate
that
newly
ring
fusion
carborane,
pyridyl
is
non-aromatic.
However,
not
only
leads
1H
chemical
shift
considerably
downfield
shifted
owing
strong
diatropic
current
embedded
but
also
devotes
new/improved
physicochemical
properties
including
increased
thermal
stability,
emergence
absorption
band,
largely
red-shifted
emission
band
enhanced
efficiency.
Besides,
number
bright,
color-tunable
solid
emitters
spanning
over
all
visible
light
obtained
absolute
luminescence
efficiency
61%,
contrast
aggregation-caused
quenching
of,
e.g.,
Rhodamine
B
containing
2D-aromatics-fused
structure.
This
work
demonstrates
hybrid
conjugated
might
promising
scaffolds
construction
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(11), С. 7791 - 7802
Опубликована: Март 10, 2024
The
development
of
new
synthetic
methods
for
B–H
bond
activation
has
been
an
important
research
area
in
boron
cluster
chemistry,
which
may
provide
opportunities
to
broaden
the
application
scope
clusters.
Herein,
we
present
a
reaction
strategy
direct
site-selective
functionalization
nido-carboranes
initiated
by
photoinduced
cage
via
noncovalent
cage···π
interaction.
As
result,
nido-carborane
radical
is
generated
through
single
electron
transfer
from
3D
2D
photocatalyst
upon
irradiation
with
green
light.
resulting
transient
could
be
directly
probed
advanced
time-resolved
EPR
technique.
In
air,
subsequent
transformations
active
have
led
efficient
and
selective
B–N,
B–S,
B–Se
couplings
presence
N-heterocycles,
imines,
thioethers,
thioamides,
selenium
ethers.
This
protocol
also
facilitates
both
late-stage
modification
drugs
synthesis
nido-carborane-based
drug
candidates
neutron
capture
therapy
(BNCT).
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(20)
Опубликована: Фев. 11, 2022
Abstract
Carboranes
are
boron–carbon
molecular
clusters
that
possess
unique
properties,
such
as
their
icosahedron
geometry,
high
boron
content,
and
delocalized
three‐dimensional
aromaticity.
These
features
render
carboranes
valuable
building
blocks
for
applications
in
supramolecular
design,
nanomaterials,
optoelectronics,
organometallic
coordination
chemistry,
neutron
capture
therapy
(BNCT)
agents.
Despite
tremendous
progress
this
field,
stoichiometric
chemical
redox
reagents
largely
required
the
oxidative
activation
of
carborane
cages.
In
context,
electrosyntheses
represent
an
alternative
strategy
more
sustainable
syntheses.
It
is
only
recent
few
years
considerable
has
been
made
electrochemical
cage
functionalization
carboranes,
which
summarized
Minireview.
We
anticipate
electrocatalysis
will
serve
increasingly
powerful
stimulus
within
current
renaissance
electrochemistry.
Frontiers in Chemistry,
Год журнала:
2024,
Номер
12
Опубликована: Ноя. 5, 2024
Icosahedral
boron
clusters-based
BODIPY
dyes
represent
a
cutting-edge
class
of
compounds
that
merge
the
unique
properties
clusters
with
exceptional
fluorescence
characteristics
dyes.
These
kinds
molecules
have
garnered
substantial
interest
due
to
their
potential
applications
across
various
fields,
mainly
including
optoelectronics,
bioimaging,
and
use
as
carriers
for
Boron
Neutron
Capture
Therapy
(BNCT).
Carborane
are
known
stability,
rigid
geometry,
3D-aromaticity,
while
renowned
strong
absorption,
high
quantum
yields,
photostability.
The
integration
carborane
into
structures
leverages
stability
versatility
carboranes
enhancing
photophysical
BODIPY-based
fluorophores.
This
review
explores
synthesis
structural
diversity
dyes,
highlighting
how
incorporation
can
lead
significant
changes
in
electronic
optical
We
discuss
enhanced
characteristics,
such
red-shifted
absorption
emission
poperties,
charge
transfer
effects,
improved
cellular
uptake,
resulting
from
substitution.
also
delves
diverse
these
compounds.
In
carborane-BODIPY
offer
superior
internalization,
making
them
ideal
cell
tracking.
photodynamic
therapy,
(PDT)
act
potent
photosensitizers
capable
generating
reactive
oxygen
species
(ROS)
targeted
cancer
treatment
excellent
candidates
PDT.
Additionally,
make
suitable
optoelectronic
applications,
organic
light-emitting
diodes
(OLEDs)
sensors.
Overall,
versatile
promising
materials
innovation
scientific
technological
applications.
aims
provide
comprehensive
overview
current
state
research
on
synthesis,
properties,
broad
application
spectrum.
Inorganics,
Год журнала:
2023,
Номер
11(2), С. 72 - 72
Опубликована: Фев. 2, 2023
This
review
summarizes
data
on
the
main
types
of
charge-compensated
nido-carborane
derivatives.
Compared
with
organic
analogs,
onium
derivatives
have
increased
stability
due
to
stabilizing
electron-donor
action
boron
cage.
Charge-compensated
are
considered
according
type
heteroatom
bonded
a
atom.
Angewandte Chemie International Edition,
Год журнала:
2020,
Номер
60(14), С. 7838 - 7844
Опубликована: Дек. 29, 2020
Abstract
An
atom‐economical
method
for
the
direct
B−H
functionalization
of
nido
‐carboranes
(7,8‐
‐C
2
B
9
H
12
−
)
has
been
developed
under
electrochemical
reaction
conditions.
In
this
system,
anodic
oxidation
serves
as
a
green
alternative
traditional
chemical
oxidants
in
‐carboranes.
No
transition‐metal
catalyst
is
required
and
different
heteroatoms
bearing
lone
pair
are
reactive
transformation.
Coupling
with
thioethers,
selenides,
tellurides,
N‐heterocycles,
phosphates,
phosphines,
arsenides
antimonides
demonstrates
high
site‐selectivity
efficiency.
Importantly,
can
be
easily
incorporated
into
drug
motifs
through
protocol.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(33)
Опубликована: Июнь 6, 2022
Abstract
The
classical
aggregation‐induced
emission
(AIE)‐active
luminogens
(AIEgens)
usually
include
two‐dimensional
aromatic
systems
such
as
tetraphenylethenes,
which
are
synthesized
in
several
steps
by
using
toxic
additives.
Here,
we
proposed
a
new
molecular
design
strategy
for
the
realization
of
AIE
properties
combining
three‐dimensional
boron
clusters
carboranes
with
vinyl
group(s).
To
obtain
library
cluster‐based
AIEgens,
Pd‐catalyzed
hydroboration
alkynes
is
reported.
This
reaction
protocol
proceeds
one
step
under
mild
conditions
rapid
rate,
excellent
yields
and
regioselectivity.
Photophysical
property
studies
demonstrate
that
facile
motions
solution
can
be
inhibited
solid
state
these
molecules,
leads
to
interesting
properties.
work
provides
not
only
general
principle
AIEgens
but
also
an
efficient
methodology
synthesize
photo‐functional
molecules.
Organic Letters,
Год журнала:
2022,
Номер
24(7), С. 1507 - 1512
Опубликована: Фев. 10, 2022
An
efficient
Rh-catalyzed
B(4)-H
and
B(3)-H
alkylation
reaction
was
demonstrated
from
the
reactions
of
a
variety
pyridyl
o-carboranes
with
α-diazodicarboxylates
release
molecular
nitrogen,
leading
to
production
alkylated
in
good
excellent
yields
high
selectivity,
wide
substrate
scope,
functional
group
tolerance.
Chemical Science,
Год журнала:
2024,
Номер
15(24), С. 9274 - 9280
Опубликована: Янв. 1, 2024
Broadening
carborane
applications
has
consistently
been
the
goal
of
chemists
in
this
field.
Herein,
compared
to
alkyl
or
aryl
groups,
a
cage
demonstrates
an
advantage
stabilizing
unique
bonding
interaction:
M⋯C–H
interaction.