18-membered
diazomacrocycles
with
imidazole
or
4-methylimidazole
residue
as
a
part
of
macrocycle
were
used
chromoionophores
in
bismuth(III)
and
lead(II)
dual
selective
optodes
for
the
first
time.
Cellulose
triacetate
membranes
doped
macrocyclic
are
color
change
from
orange/red
to
different
shades
blue
violet,
respectively.
Results
obtained
model
real
samples
showed
that
easily
accessible
regenerable
sensor
materials
can
be
spectrophotometric
colorimetric
detection
determination
lead(II).
The
LOD
values
1.63×10-7
M
3.03×10-7
detection,
respectively,
when
using
optode
residue.
For
sensing
material
macroring
lowest
limits
lead(II):
2.14×10-7
3.99×10-7
digital
analysis
mode
Chemical Society Reviews,
Journal Year:
2024,
Volume and Issue:
53(9), P. 4786 - 4827
Published: Jan. 1, 2024
This
review
summarizes
structural
and
synthetic
aspects
of
heterocyclic
molecules
incorporating
an
atom
a
hypervalent
main-group
element.
The
higher
thermal
stability
heterocycles,
as
compared
to
their
acyclic
analogs,
adds
special
feature
chemistry.
Dalton Transactions,
Journal Year:
2024,
Volume and Issue:
53(28), P. 11858 - 11866
Published: Jan. 1, 2024
Seven-coordinated
hypervalent
tin(
iv
)
compounds
with
large
binding
constants
were
prepared
and
applied
for
vapochromic
thermochromic
π-conjugated
polymer
films.
RSC Mechanochemistry,
Journal Year:
2024,
Volume and Issue:
1(4), P. 322 - 327
Published: Jan. 1, 2024
We
demonstrated
solvent-
and
catalyst-free
mechanochemical
synthesis
of
hypervalent
tin(
iv
)
compounds
for
luminescent
materials
without
purification.
Bulletin of the Chemical Society of Japan,
Journal Year:
2023,
Volume and Issue:
96(8), P. 778 - 784
Published: July 13, 2023
Abstract
NIR-light
emitting
materials
are
significant
as
a
source
for
technology.
Previously,
we
have
found
that
hypervalent
germanium-fused
azobenzene
(GAz)
compounds
showed
NIR
emissions
despite
the
small
π-conjugated
systems
owing
to
trigonal
bipyramidal
geometry
with
three-center
four-electron
(3c-4e)
bonds.
Herein,
succeed
in
enhancing
their
luminescence
properties
by
introduction
of
electron-donating
groups.
It
is
revealed
frontier
molecular
orbitals
bonds
can
be
varied
depending
on
type
substituents.
As
result,
GAz
compound
diphenylamine
groups
shows
efficient
emission
at
room
temperature
(λPL
=
761
nm
and
ΦPL
0.07)
77
K
749
0.20).
Furthermore,
data
from
theoretical
calculations
support
experimental
results
provide
additional
information
producibility
compounds.
Our
findings
afford
strategies
expand
library
fine-tunable
NIR-luminescent
involving
heteroatoms.
Inorganic Chemistry,
Journal Year:
2024,
Volume and Issue:
63(27), P. 12417 - 12425
Published: June 26, 2024
Structure,
stability,
and
electronic
properties
of
the
bimetallic
{[IrI(terpy)(Me)]-[BiIIINNN]}n
monomeric,
oligomeric,
polymeric
structures
(n
=
1–3
∞;
terpy
terpyridine;
Me
methyl;
BiNNN
bismuth
triamide)
their
derivatives
(designated
as
(Bi·Ir)n
structures)
were
studied
theoretically
by
DFT
cluster
periodic
calculations.
Stable
Bi·Ir
adducts
(monomers)
formed
with
short
Bi–Ir
bonds
(<2.7
Å)
Gibbs
free
binding
energies
larger
than
20
kcal/mol
for
all
systems.
The
substitution
pincer
ligands
Ir(I)
Bi(III)
complexes
electron-donating
(NH2)
electron-withdrawing
(NO2,
F,
CF3)
groups,
respectively,
enhanced
Ir
→
Bi
charge
transfer,
substantially
stabilizing
monomers.
monomers
from
unsubstituted
can
be
considered
dispersion
stabilized
adducts,
they
may
form
spontaneously
layered
oligomers/polymers
semiconducting
properties.
self-assembly
into
is
hindered
bulkier
protecting
groups
on
complex,
such
tBu
SiMe3.
European Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
27(45)
Published: Aug. 20, 2024
Abstract
The
unique
optical
properties
created
by
the
combination
of
azobenzene‐based
π‐conjugated
systems
and
hypervalent
bonds
are
summarized.
bond,
a
polarized
three‐center
four‐electron
(3c−4e)
simultaneously
provides
electron‐donating
‐withdrawing
effects
to
directly
attached
system.
resulting
compounds
have
dramatically
narrow
energy
gap
showing
near‐infrared
(NIR)
emission
despite
limited
size
systems.
In
addition,
also
exhibit
stimuli‐responsive
chromism
through
reversible
coordination‐number
shift
central
main‐group
elements
in
both
crystals
polymer
films.
We
explain
that
nature
depends
on
element
type,
which
is
particularly
effective
bringing
out
heavy
elements.
this
review,
we
describe
use
novel
strategy
not
only
for
manipulating
levels
system
but
developing
variety
functional
materials
based
newly
rising
from
element.
Smart Molecules,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 16, 2025
Abstract
In
this
review,
the
synthesis,
functions,
and
applications
of
polymers
containing
germanium
tin,
which
are
heavy
group
14
elements,
in
their
polymer
frameworks
summarized.
Germanium
tin
can
form
similar
skeletal
structures
with
homologues
carbon
silicon,
whereas
show
unique
properties
derived
from
large
atomic
radii
weak
binding
energies.
For
example,
polygermane
polystannane
exhibited
light
absorption
UV–visible
region
conductivity
because
σ‐conjugation
through
main‐chain
constructed
by
σ‐bonds
between
elements.
The
was
affected
conformational
change
main‐chain,
thermochromic
be
induced.
Furthermore,
bonds
were
able
to
cleaved
homolytically
upon
photoirradiation,
radicals
subsequently
generated.
By
incorporating
hypervalent
elements
into
π‐conjugated
system,
it
possible
modulate
electronic
system
σ*–π*
conjugation
highly
coordinated
Finally,
for
organic
solar
cells,
light‐emitting
materials,
chemical
sensors
have
been
achieved.
Herein,
representative
synthetic
methods
creating
smart
materials
will
explained.
