Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(47)
Published: Aug. 12, 2024
Abstract
In
the
deep‐ultraviolet
(DUV)
region,
nonlinear
optical
(NLO)
crystals
must
meet
stringent
requirements,
including
a
large
band
gap
and
sufficient
second
harmonic
generation
(SHG)
response.
Typically,
these
criteria
are
fulfilled
by
borates,
carbonates
nitrates
containing
π‐conjugated
groups.
contrast,
sulfates
phosphates,
with
polarizabilities
significantly
smaller
than
those
of
groups,
struggle
to
achieve
similar
performance.
Here,
we
present
discovery
Mg
2
PO
4
Cl,
magnesium‐based
phosphate,
identified
from
over
10,000
phosphates
based
on
polar‐axial‐symmetry
screening
strategy,
which
exhibits
highest
SHG
response
(5.2×KH
(KDP))
phase‐matching
ability
among
non‐π‐conjugated
DUV
transparent
NLO
crystals.
This
compound
belongs
Pna
1
space
group,
[PO
]
units
consistently
aligned
along
screw
axis
glide
planes
throughout
its
crystal
structure.
Theoretical
calculations
attribute
remarkable
effect
orderly
arrangement
heteroanionic
[MgO
5
Cl]
Cl
polyhedra
alongside
isolated
tetrahedra,
supported
Berry
phase
analysis.
Furthermore,
crystallographic
structure
analysis
significant
effects
validates
effectiveness
our
strategy.
These
findings
offer
valuable
insights
into
origins
in
compounds
both
material
design
structural
chemistry
perspective,
inspiring
future
efforts
revitalize
phosphates.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(47)
Published: Aug. 12, 2024
Abstract
In
the
deep‐ultraviolet
(DUV)
region,
nonlinear
optical
(NLO)
crystals
must
meet
stringent
requirements,
including
a
large
band
gap
and
sufficient
second
harmonic
generation
(SHG)
response.
Typically,
these
criteria
are
fulfilled
by
borates,
carbonates
nitrates
containing
π‐conjugated
groups.
contrast,
sulfates
phosphates,
with
polarizabilities
significantly
smaller
than
those
of
groups,
struggle
to
achieve
similar
performance.
Here,
we
present
discovery
Mg
2
PO
4
Cl,
magnesium‐based
phosphate,
identified
from
over
10,000
phosphates
based
on
polar‐axial‐symmetry
screening
strategy,
which
exhibits
highest
SHG
response
(5.2×KH
(KDP))
phase‐matching
ability
among
non‐π‐conjugated
DUV
transparent
NLO
crystals.
This
compound
belongs
Pna
1
space
group,
[PO
]
units
consistently
aligned
along
screw
axis
glide
planes
throughout
its
crystal
structure.
Theoretical
calculations
attribute
remarkable
effect
orderly
arrangement
heteroanionic
[MgO
5
Cl]
Cl
polyhedra
alongside
isolated
tetrahedra,
supported
Berry
phase
analysis.
Furthermore,
crystallographic
structure
analysis
significant
effects
validates
effectiveness
our
strategy.
These
findings
offer
valuable
insights
into
origins
in
compounds
both
material
design
structural
chemistry
perspective,
inspiring
future
efforts
revitalize
phosphates.
Chemical Science,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 1, 2025
The
[TeS
3
]
2−
unit
with
a
SCALP
disrupts
tetrahedral
symmetry,
leading
to
the
synthesis
of
Cu
10
Te
4
S
13
for
first
time.
This
material
exhibits
strong
SHG
(3.75
×
AgGaS
2
)
and
widest
MFIR
transparency
(2.5–25
μm)
reported
NLO
chalcogenides.
Journal of Materials Chemistry C,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 1, 2025
Hg
2
(SeO
3
)(TeO
),
a
new
tellurite–selenite
birefringent
crystal,
showcases
broad
transparency
range,
large
birefringence,
and
high
thermal
stability,
positioning
it
as
promising
material.
Abstract
Phosphate
crystals
are
known
for
their
low
birefringence,
a
result
of
the
symmetrical
tetrahedral
structure
PO
4
groups.
Attempts
to
increase
birefringence
have
traditionally
involved
incorporation
highly
anisotropic
ions
and
Yet,
majority
modified
phospates
still
exhibit
value
below
0.1,
due
counteracting
effects
elements
within
coordination.
The
present
study
has
first
time
discovered
novel
birefringence‐active
Hg
I
2
II
O
9
unit
successfully
constructed
layered
structure,
which
ingeniously
prevents
mutual
cancellation
effects.
This
synthesis
(Te
)
(HPO
confirms
effectiveness
this
strategy,
yielding
0.444
at
546
nm,
outperforms
99%
phosphate
surpasses
that
commercial
counterparts
like
YVO
(0.209@1064
nm)
CaCO
3
(0.175@533
nm).
Structural
analysis
PAWED
calculations
indicate
significant
is
attributed
synergistic
interaction
between
(23.76%),
HPO
tetrahaedron
(24.24%)
TeO
group
(51.99%).
breakthrough
paves
way
phosphates
meet
demands
modern
technological
advancements,
expanding
potential
applications
in
field
optics.
Advanced Optical Materials,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 17, 2025
Abstract
The
hydrothermal
synthesis
and
characterization
of
a
novel
bismuth
molybdenum
selenite
material,
Bi
2
F
(MoO
3
)
(SeO
·H
O,
designed
using
chemical
substitution‐based
approach,
is
reported.
This
material
represents
the
first
example
its
kind
in
Bi–Mo–Se
system,
providing
new
insights
into
noncentrosymmetric
(NCS)
crystal
engineering.
compound
exhibits
outstanding
nonlinear
optical
(NLO)
properties,
including
second‐harmonic
generation
(SHG)
efficiency
1.2
times
that
KTiOPO₄
birefringence
0.118
at
546.1
nm.
Additionally,
it
demonstrates
wide
transparency
range
(0.36–10
µm),
making
promising
candidate
for
advanced
NLO
applications.
Structural
computational
analyses
show
remarkable
SHG
response
driven
by
highly
distorted
MoO₆
octahedra,
strong
interatomic
interactions
within
1D
chains,
polarizable
⁺
SeO₃
groups.
Furthermore,
thermally
stable
after
dehydration
affinity
occupying
void
space
5‐membered
ring
(5‐MR).
These
findings
open
avenues
design
NCS
materials
with
enhanced
functionalities,
offering
significant
potential
development
solid‐state
materials.
Inorganic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 21, 2025
In
the
field
of
structural
chemistry,
crystals
containing
[OM4]
tetrahedra
(M
=
metal
cation)
structure
have
been
well
documented.
However,
compounds
both
[OPb4]
and
π-conjugated
groups
are
less
reported
due
to
their
complexity.
this
work,
a
new
lead
borate–nitrate,
Pb9O4(BO3)2(NO3)4,
has
synthesized
by
high
temperature
melt
method.
Notably,
Pb9O4(BO3)2(NO3)4
contains
special
[O8Pb18]∞
chains
formed
tetrahedra.
This
compound
possesses
large
optical
anisotropy
with
birefringence
Δn
0.117
at
546
nm.
Inorganic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 14, 2025
For
ultraviolet
(UV)
nonlinear
optical
(NLO)
crystals,
three
fundamental
parameters
are
essential:
the
absorption
edge,
NLO
coefficient,
and
shortest
wavelength
for
second
harmonic
generation
(SHG)
phase
matching
(PM).
In
this
study,
a
rare-earth
borate,
Rb7PbY2(B5O10)3,
was
synthesized
via
chemical
cosubstitution
using
high-temperature
melt
method.
Rb7PbY2(B5O10)3
has
been
found
to
crystallize
with
noncentrosymmetric
(NCS)
space
group
an
SHG
intensity
of
1.3
times
KDP
UV
cutoff
edge
less
than
300
nm.
These
properties
indicate
that
exhibits
significant
potential
as
material.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 7, 2025
In
the
exploration
of
nonlinear
optical
(NLO)
materials,
developing
new
functional
groups
for
high
performance
is
essential.
Achieving
a
balance
among
band
gap,
second
harmonic
generation
(SHG),
and
birefringence
within
compound
quite
challenging.
By
directly
connecting
iodates
borates
by
B-O-I
bridges,
two
boroiodates
with
novel
[B3IO8(OH)]3-
[B4IO11]5-
anionic
groups,
namely,
Na[B3IO7(OH)]
(NBIO-I)
Na2[B4IO9](IO3)
(NBIO-II),
were
successfully
synthesized
first
time
through
boric
acid
melting
method
under
different
molar
ratios
H3BO3/NaIO3.
NBIO-I
(Pbca)
features
unique
1D
∞1[B3IO7(OH)]-
chain
composed
corner-sharing
[B3O6(OH)]4-
[IO3]-
hanging
on
both
sides
chain.
contrast,
NBIO-II
(Cc)
displays
2D
layer
∞2[B4IO9]-,
in
which
all
are
same
side
∞2[B4O7]2-
formed
[B3O7]5-
[BO3]3-
groups.
Remarkably,
exhibits
wide
gap
(4.3
eV),
large
(0.298@546
nm),
strongest
SHG
response
(7.8
×
KDP)
borate-iodates
reported
previously.
This
work
not
only
discovered
as
promising
NLO
crystals
but
also
provided
an
effective
synthetic
route
excellent
properties.
