Angewandte Chemie,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 23, 2024
Abstract
Advancing
laser
technologies
requires
maximizing
the
anisotropy
of
crystalline
media
and
overcoming
current
birefringence
limitations.
We
introduce
strategy
linear
π
group
anisotropic
structure
building
units
(ABUCB),
leading
to
an
unprecedented
large
(Δ
n
),
a
record‐high
Δ
obv.
0.152
in
sodium
bis(dicyanoborato)fluoride
(Na[BF
2
(CN)
]),
highest
reported
among
deep
ultraviolet
(DUV)
materials.
This
value
is
35
%
greater
than
state‐of‐the‐art
α
‐BBO
1167
MgF
.
Density
functional
theory
analyses
suggest
that
enhances
bulk
optical
ensures
shorter
DUV
absorption
edge.
These
results
establish
Na[BF
]
as
groundbreaking
birefringent
material
open
new
avenues
for
research
into
extending
groups
exploring
additional
possibilities.
Chemical Science,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 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.
Advanced Science,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 28, 2025
Abstract
In
the
search
for
new
ultraviolet
(UV)
nonlinear
optical
(NLO)
materials,
two
novel
cadmium
mixed
halide
compounds,
(NH
4
)
2
Cd
Cl
3
F
and
Br
,
are
successfully
synthesized
via
hydrothermal
methods.
These
compounds
crystallize
in
noncentrosymmetric
(NCS)
space
group,
R
32,
composed
of
distorted
octahedral
[CdX
]
(X═Cl
or
Br)
units,
which
extend
into
a
3D
framework.
Remarkably,
both
demonstrate
strong
second‐harmonic
generation
(SHG)
efficiencies—3.0
8.0
times
that
KH
PO
Cl‐
Br‐containing
analogs,
respectively—with
phase‐matching
behavior
observed.
The
SHG
efficiency
is
attributed
to
highly
coordination
environment
polarizable
d
10
2+
ions,
with
benefiting
further
from
Br's
greater
polarizability.
Furthermore,
these
exhibit
wide
bandgaps
exceeding
4.2
eV,
making
them
first
metal
systems
incorporating
fluoride
suitable
UV
NLO
applications.
With
absorption
cut‐off
edges
as
short
203
nm
243
materials
represent
significant
advancement
development
UV‐transparent
materials.
This
study
introduces
synthetic
strategy
design
enhanced
properties,
offering
promising
candidates
future
technologies.
Inorganic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 21, 2025
Herein,
we
prepared
two
novel
hydrogen-bonded
supramolecular
frameworks
within
the
Mg-pyridine
dicarboxylic
acid
(Mg-PDA)
system:
[Mg(H2O)6][(C7H4NO4)·H2O]2
(1)
and
Mg(C7H3NO4)(H2O)2
(2).
In
compound
1,
2D
[(C7H4NO4)·H2O]∞–
anionic
layer
is
formed
by
O/N–H···O
hydrogen
bonding
connecting
(C7H4NO4)−
anions
with
free
water
molecules.
contrast,
[Mg(C7H3NO4)(H2O)2]∞
neutral
in
2
connected
Mg–O/N
coordination
bonds,
which
promote
coplanar
arrangement
of
π-conjugated
six-membered
pyridine
rings.
This
structural
enhances
disparity
between
in-plane
out-of-plane
interactions
[Mg(C7H3NO4)(H2O)2]
layer.
Consequently,
both
experimental
data
theoretical
calculations
indicate
that
shows
strong
optical
anisotropy,
giant
birefringence
(Δn
=
0.44
@
546
nm)
surpassing
1
0.34
exceeding
commercially
available
α-BaB2O4
0.122
nm).
More
importantly,
combination
their
short-wave
UV
cutoff
edges
(279
nm
for
273
2),
features
most
promising
birefringent
properties
among
all
Mg-containing
crystals.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 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.
Angewandte Chemie,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 29, 2025
Abstract
The
simultaneous
optimization
of
large
birefringence
(Δn,
a
linear
optical
property)
and
strong
second‐harmonic
generation
(SHG,
nonlinear
(NLO)
in
single
crystal
remains
significant
challenge
due
to
the
inherently
distinct
structural
requirements
for
these
properties.
Although
nonbonding
electrons
have
been
extensively
studied
oxides
chalcogenides,
research
has
predominantly
focused
on
their
role
along
polar
axes,
leaving
influence
axes
tetrahedral
stacking
largely
unexplored.
Herein,
we
propose
electron‐inversion
strategy
overcome
phase‐matching
limitations
defect
diamond‐like
structures.
By
incorporating
T2‐[Ga
4
S
10
]
supertetrahedral
motifs,
successfully
synthesized
[Ba
Cl
2
][CdGa
(space
group:
I
),
which
exhibits
219%
enhancement
Δn
compared
nonphase‐matching
parent
structure
Cd
GaS
.
weakly
bound
electrons,
governed
by
atomic
potentials,
demonstrate
SHG
responses
under
fields.
compound
not
only
achieves
broad
transmission
range
(0.28–18.6
µm)
high
laser‐induced
damage
threshold
(40.1
×
AgGaS
)
but
also
optimally
balances
wide
bandgap
(
E
g
=
3.58
eV)
response
(1.4
representing
one
best‐performing
Cd‐based
materials
date.
This
work
introduces
first
design
based
electron‐driven
structure–property
relationships,
providing
critical
insights
rational
high‐performance
NLO
materials.
Advanced Optical Materials,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 29, 2025
Abstract
The
ideal
foundation
for
constructing
nonlinear
optical
(NLO)
and
birefringent
materials
is
provided
by
planar
π‐conjugated
units
with
high
hyperpolarizability
anisotropy.
However,
the
bandgap
diminishes
number
of
functional
joined
covalent
bonds,
making
their
employment
challenging
in
short‐wavelength
spectral
region.
To
overcome
this
limitation,
a
strategy
devised
that
assembles
different
via
hydrogen
bonding.
By
using
[C
3
H
x
O
4
]
(
=
2–4),
[CN
7
],
6
as
fundamental
building
blocks
omitting
metal
cations,
six
compounds
are
effectively
synthesized.
][C
exhibits
moderate
second
harmonic
generation
(SHG)
response
(1.2
×
KDP)
along
shortest
phase‐matching
wavelength
255
nm.
Additionally,
2
display
significant
birefringence
0.209
0.182
at
1064
nm,
respectively,
possess
short
cutoff
edges
233
200
indicating
potential
ultraviolet
NLO
materials.
This
study
confirms
role
bonding
structural
rearrangement,
which
thereby
reinforces
properties.
Inorganic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Май 28, 2025
The
exploration
of
ultraviolet
(UV)
nonlinear
optical
(NLO)
crystals
owning
a
strong
second-harmonic
generation
(SHG)
response
has
consistently
been
difficult
task.
Herein,
we
have
controllably
tailored
the
lead-oxychloride
polyhedron
by
tuning
amount
KCl
under
mixed-solvothermal
conditions
to
afford
new
UV
NLO
crystal,
K3[Pb2Cl5(HCOO)2]·H2O.
Interestingly,
benefiting
from
oriented
arrangement
large
[Pb6Cl24O12]
rings,
microscopic
second-order
susceptibilities
distorted
[PbCl5O2]
polyhedrons
are
effectively
superimposed.
Remarkably,
K3[Pb2Cl5(HCOO)2]·H2O
owns
unique
3D
polar
framework,
phase-matchable
SHG
that
is
3.1
times
as
KDP,
suitable
birefringence
0.108@1064
nm,
broad
high
transparent
window
extending
340
nm
in
region,
and
feasible
crystal
growth.
Dipole
moment
theoretical
calculations
elucidate
originates
polyhedron.
This
study
will
shed
light
on
development
subsequent
crystals.
Chemistry - A European Journal,
Год журнала:
2024,
Номер
31(8)
Опубликована: Ноя. 21, 2024
Abstract
Deep
ultraviolet
(DUV)
nonlinear
optical
(NLO)
crystals
with
balanced
performance
are
crucial
for
extending
laser
wavelengths
into
the
DUV
region,
essential
various
applications.
However,
developing
ideal
is
challenging
due
to
stringent
requirements:
strong
second‐harmonic
generation
(SHG)
response,
short
cut‐off
wavelength,
and
effective
phase‐matching
behavior.
NLO
borates,
which
feature
π‐conjugated
groups,
have
garnered
attention
their
higher
SHG
coefficients
compared
phosphates.
phosphates
typically
show
UV
edges
large
HOMO‐LUMO
gap
(approximately
9.6
eV)
of
[PO₄]
units.
To
enhance
effect
while
maintaining
transparency
in
phosphates,
several
strategies
been
proposed:
1)
using
distorted
polymerized
P−O
groups
like
isolated
C₁‐[P₃O₁₀]⁵
−
[P₂O₇]⁴
;
2)
aligning
3−
tetrahedra
along
polar
screw
axis;
3)
introducing
additional
NLO‐active
units;
4)
exploring
new
units
derived
from
,
such
as
[PO₃F]
2−
tetrahedra.
These
led
successful
development
non‐centrosymmetric
highlighting
potential
candidates.
This
review
explores
relationship
between
crystal
structures
performance,
proposes
future
directions
materials.
Advanced Optical Materials,
Год журнала:
2024,
Номер
unknown
Опубликована: Сен. 19, 2024
Abstract
Non‐centrosymmetric
organics
are
promising
nonlinear
optical
(NLO)
candidates,
which
always
exhibit
a
short
UV
absorption
cutoff
edge,
and
strong
second
harmonic
generation
(SHG)
response,
but
an
overlarge
birefringence.
Here,
in
order
to
optimize
the
birefringence,
methyl
modulation
of
π‐conjugated
organic
planar
units
is
proposed
implemented
with
urea
structure
as
template.
Thus,
N
‐methylurea
N,N'
‐dimethylurea
crystals
obtained
by
partially
replacing
hydrogen
atoms
groups.
This
replacement
reduces
donors
weakens
interchain
bonds,
facilitates
decreasing
density
parallel
arrangement
units.
Hence,
both
not
only
optimized
birefringence
(
≈0.099
≈0.072
at
546
nm)
also
enhanced
SHG
response
≈1.2
×
β
‐BaB
2
O
4
≈1.9
),
while
maintaining
edge.
Therefore,
this
work
provides
novel
strategy
for
structural
design
performance
NLO
crystals.