Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(44)
Published: July 10, 2024
Abstract
Anisotropy
is
crucial
for
birefringence
(Δ
n
)
in
optical
materials,
but
optimizing
it
remains
a
formidable
challenge
>0.3).
Supramolecular
frameworks
incorporating
π‐conjugated
components
are
promising
achieving
enhanced
because
of
their
structural
diversity
and
inherent
anisotropy.
Herein,
we
first
synthesized
(C
6
H
NO
2
+
Cl
−
(
NAC
then
constructed
halogen‐bonded
supramolecular
framework
I
4
INA
by
halogen
aliovalent
substitution
with
.
The
organic
moieties
protonated
deprotonated
nicotinic
acid
NA
),
respectively.
antiparallel
arrangement
birefringent‐active
units
leads
to
significant
differences
the
bonding
characteristics
between
interlayer
intralayer
domains.
Moreover,
[O⋅⋅⋅I
⋅⋅⋅N]
bond
1D
[I
]
chain
exhibits
stronger
interactions
stricter
directionality,
resulting
more
pronounced
in‐plane
anisotropy
intrachain
interchain
directions.
Consequently,
exceptional
birefringent
performance,
value
0.778
at
550
nm,
twice
that
(0.363
nm).
This
significantly
exceeds
those
commercial
crystals,
such
as
CaCO
3
(0.172
546
nm),
highest
reported
among
ultraviolet
crystals.
work
presents
novel
design
strategy
employs
bonds
connection
sites
modes
units,
opening
new
avenues
developing
high‐performance
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(11), P. 7868 - 7874
Published: March 8, 2024
Sulfate
crystals
are
often
criticized
for
their
low
birefringence.
The
small
anisotropic
SO4
group
is
becoming
the
biggest
bottleneck
hindering
application
of
sulfates
in
optical
functional
materials.
In
this
study,
we
report
a
new
method
to
significantly
enhance
birefringence
sulfates.
title
compound
increases
recording
0.542@546
nm,
which
larger
than
that
commercial
birefringent
crystal
TiO2
([email protected]
nm).
At
infrared
wavelength,
Hg4(Te2O5)(SO4)
can
be
up
0.400@1064
also
much
YVO4
(0.209@1064
addition,
it
has
wide
transparency
range,
high
thermal
stability,
and
excellent
environmental
making
potential
material.
features
novel
two-dimensional
layered
structure
composed
[Hg4(Te2O5)]2+
layers
separated
by
isolated
(SO4)2–
tetrahedra.
This
was
designed
introducing
highly
selective
cation
tellurite
sulfate
system.
valence
coordination
cations
connect
with
groups
only,
structure.
steric
repulsive
action
tetrahedra
may
regulate
linear
lone
pair
arranged
way
favors
large
proven
theoretical
calculations.
PAWED
studies
showed
originated
from
synergistic
effect
(Hg2O2)2–,
(Te2O5)2–,
units,
contribution
ratio
42.17,
37.92,
19.88%,
respectively.
Our
work
breaks
limitation
opens
possibilities
as
crystals.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(14), P. 9975 - 9983
Published: March 11, 2024
Oxides
have
attracted
considerable
attention
owing
to
their
potential
for
nonlinear
optical
(NLO)
applications.
Although
significant
progress
has
been
achieved
in
optimizing
the
structural
characteristics
of
primitives
(corresponding
simplest
constituent
groups,
namely,
cations/anions/neutral
molecules)
comprising
crystalline
oxides,
role
primitives'
interaction
determining
resultant
functional
structure
and
properties
long
underappreciated
remains
unclear.
In
this
study,
we
employ
a
π-conjugated
organic
primitive
confinement
strategy
manipulate
interactions
between
antimonates
thereby
significantly
enhance
nonlinearity.
Chemical
bonds
relatively
weak
H-bonding
promote
formation
cis-
trans-Sb(III)-based
dimer
configurations
(C5H5NO)(Sb2OF4)
(4-HPYSOF)
(C5H7N2)(Sb2F7)
(4-APSF),
respectively,
resulting
very
different
second-harmonic
generation
(SHG)
efficiencies
birefringences.
particular,
4-HPYSOF
displays
an
exceptionally
strong
SHG
response
(12
×
KH2PO4
at
1064
nm)
large
birefringence
(0.513
546
Sb(III)-based
NLO
oxide
as
well
UV
cutoff
edge.
Structural
analyses
theoretical
studies
indicate
that
polarized
ionic
bond
facilitate
favorable
arrangement
both
inorganic
primitives,
enhancing
nonlinearity
4-HPYSOF.
Our
findings
shed
new
light
on
intricate
correlations
configuration,
properties,
and,
more
broadly,
our
approach
provides
perspective
development
advanced
materials
through
interatomic
engineering
oxides.
Materials Horizons,
Journal Year:
2024,
Volume and Issue:
11(7), P. 1704 - 1709
Published: Jan. 1, 2024
For
non-centrosymmetric
(NCS)
oxides
intended
for
ultraviolet
(UV)
nonlinear
optical
(NLO)
applications,
achieving
a
wide
band
gap,
large
second
harmonic
generation
(SHG)
intensity,
and
sufficient
birefringence
to
satisfy
phase
matching
is
significant
challenge
due
their
inherent
incompatibility.
To
address
this
issue,
study
proposes
strategy
called
framework-optimized
structural
transformation.
Building
upon
centrosymmetric
(CS)
NaGa(SeO
Inorganic Chemistry,
Journal Year:
2024,
Volume and Issue:
63(9), P. 4011 - 4016
Published: Feb. 16, 2024
Exploring
new
material
systems
is
a
highly
significant
task
in
the
field
of
inorganic
chemistry.
A
mixed-valent
selenium
compound,
Hg3Se(SeO3)(SO4),
was
successfully
synthesized
through
situ
reactions.
This
compound
exhibits
novel
three-dimensional
structure
composed
Hg3Se(SO4)
layers
bridged
by
SeO3
trigonal
pyramids.
It
first
containing
(SeO3)2–,
(SO4)2–,
and
Se2–
simultaneously.
In
addition,
Hg3Se(SeO3)(SO4)
possesses
wide
bandgap
(3.5
eV),
moderate
birefringence
(Cal:0.064@546
nm,
Exp:0.069@546
nm),
high
laser-induced
damage
threshold
(23.35
MW
cm–2),
transmittance
window
(0.28–6.6
μm).
Our
work
demonstrates
that
(+4,
−2)
selenite
selenide
can
be
potential
optical
materials
for
mid-infrared
region.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(21), P. 8071 - 8079
Published: Jan. 1, 2024
A
universal
synthesis
method
for
polyfluoroantimonites
has
been
developed.
Polar
[(C
5
H
6
N
2
)
H](Sb
4
F
13
was
achieved
by
polyfluoroantimonite
strategy.
It
features
a
strong
SHG
effect,
large
birefringence
and
high
LIDT
value.
Inorganic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(6), P. 1775 - 1780
Published: Jan. 1, 2024
(NH
4
)
3
[Sn
2
(PO
]Cl:
the
rational
design
of
a
tin-based
phosphate
with
coexistence
large
optical
anisotropy
and
short-wave
ultraviolet
transparency.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(29)
Published: May 15, 2024
Abstract
Lead
halide
molecular
ferroelectrics
represent
an
important
class
of
luminescent
ferroelectrics,
distinguished
by
their
high
chemical
and
structural
tunability,
excellent
processability
distinctive
characteristics.
However,
inherent
instability,
prone
to
decomposition
upon
exposure
moisture
light,
hinders
broader
ferroelectric
applications.
Herein,
for
the
first
time,
we
present
a
series
isoreticular
metal–organic
framework
(MOF)‐type
lead
demonstrating
exceptional
robustness
under
ambient
conditions
at
least
15
months
even
when
subjected
aqueous
boiling
conditions.
Unlike
conventional
metal‐oxo
secondary
building
units
(SBUs)
in
MOFs
adopting
highly
centrosymmetric
structure
with
limited
distortion,
our
halide‐based
occupy
structurally
deformable
[Pb
2
X]
+
(X=Cl
−
/Br
/I
)
SBUs
that
facilitate
c
‐axis‐biased
displacement
Pb
2+
centers
substantially
contribute
thermoinducible
transformation.
Importantly,
this
MOF‐type
undergo
ferroelectric‐to‐paraelectric
phase
transitions
remarkably
Curie
temperature
up
505
K,
superior
most
ferroelectrics.
Moreover,
covalent
bonding
between
phosphorescent
organic
component
light‐harvesting
inorganic
achieves
efficient
spin‐orbit
coupling
intersystem
crossing,
resulting
long‐lived
afterglow
emission.
The
compelling
combination
stability,
ferroelectricity
emission
exhibited
opens
many
potential
opportunities
energy‐conversion
