Bi2(IO4)(IO3)3: A new potential infrared nonlinear optical material containing [IO4]3- anion

Article abstract of DOI:10.1021/ic201991m

A new potential infrared (IR) nonlinear optical (NLO) material Bi ₂(IO₄)(IO₃)₃ was synthesized by hydrothermal method. Bi₂(IO₄)(IO₃)₃ crystallizes in the chiral orthorhombic space group P2₁2 ₁2₁ (No. 19) with a = 5.6831(11) A, b = 12.394(3) A, and c = 16.849(3) A. It exhibits a threedimensional framework through a combination of the IO₃, IO₄, BiO₈, and BiO₉ polyhedra and is the first noncentrosymmetric (NCS) structure containing [IO₄]^3- anion. Bi₂(IO ₄)(IO₃)₃ has an IR cutoff wavelength of 12.3 ?m and belongs to the type 1 phase-matchable class with a moderately large SHG response of 5 × KDP, which is in good agreement with the theoretical calculations.

Full text of DOI:10.1021/ic201991m

Article
pubs.acs.org/IC
Bi2(IO4)(IO3)3: A New Potential Infrared Nonlinear Optical Material
Containing [IO4]3− Anion
Zhenbo Cao,†,‡,§ Yinchao Yue,†,‡ Jiyong Yao,†,‡ Zheshuai Lin,†,‡ Ran He,†,‡,§ and Zhanggui Hu*,†,‡
†Key Laboratory of Functional Crystals and Laser Technology, Technical Institute of Physics and Chemistry, Chinese Academy of
Sciences, Beijing 100190, P.R. China
‡Center for Crystal Research and Development, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences,
Beijing 100190, P.R. China
§Graduate University of the Chinese Academy of Sciences, Beijing 100049, P.R. China
S
* Supporting Information
ABSTRACT: A new potential infrared (IR) nonlinear optical (NLO) material
Bi2(IO4)(IO3)3 was synthesized by hydrothermal method. Bi2(IO4)(IO3)3
crystallizes in the chiral orthorhombic space group P212121 (No. 19) with a =
5.6831(11) Å, b = 12.394(3) Å, and c = 16.849(3) Å. It exhibits a three-
dimensional framework through a combination of the IO3, IO4, BiO8, and BiO9
polyhedra and is the first noncentrosymmetric (NCS) structure containing
[IO4]3− anion. Bi2(IO4)(IO3)3 has an IR cutoff wavelength of 12.3 μm and
belongs to the type 1 phase-matchable class with a moderately large SHG
response of 5 × KDP, which is in good agreement with the theoretical
calculations.
NaI3O8, α-Cs2(IO3)(I3O8), β-Cs2(IO3)(I3O8), and Rb2(IO3)-
(I3O8)(HIO3)2(H2O), belong to the [I3O8]− ones.11,14−16 Metal
iodates(V) have been extensively studied in the 1970s by Bell
Laboratories not only for their NLO properties, but also for
their ferroelectric, piezoelectric, and pyroelectric properties.17−23
More recently, a series of iodates with excellent SHG properties
have been synthesized in succession, including AMoO3(IO3)
(A = Rb, Cs),24 A[(VO)2(IO3)3O2] (A = NH4, Rb, Cs),25 and
RE(MoO2)(IO3)4(OH) [RE = Nd, Sm, Eu]26 by the Albrecht-
Schmitt group; α-Cs2I4O11,15 La(IO3)3,16 NaYI4O12,16 and
A2Ti(IO3)6 (A = Li, Na)27 by the Halasyamani group;
LiMoO3(IO3) by the Chen group;28 and BaNbO(IO3)5,29
INTRODUCTION
■
Nonlinear optical (NLO) materials have important applications
in laser frequency conversion, optical parameter oscillation
(OPO), and signal communication.1 According to their
transparency ranges, NLO crystals can be divided into the
ultraviolet (UV), visible, and infrared (IR) categories. Over the
past few decades, several UV and visible NLO crystals, such as
KTiOPO4 (KTP),2 LiNbO3,3 β-BaB2O4 (BBO),4 and LiB3O5
(LBO),5 have found practical applications. By contrast, IR NLO
crystals, whether they are chalcopyrites represented by AgGaX2
(X = S, Se) and ZnGeP2 or halides like CsGeBr3 and Tl4HgI6,
have shortcomings of one kind or another that have seriously
limited their applications.6,7 Therefore, in the field of
photoelectric functional materials chemistry, the search for
new types of IR NLO crystals has attracted a great deal of
research interest.8−10
We have been focused on metal iodates(V), a class of
promising IR NLO materials. There are three iodate anions of
pentavalent iodine: the widely studied [IO3]− anion and
recently studied [IO4]3− and [I3O8]− anions.11 Two
inorganic compounds of Ag4(UO2)4(IO3)2(IO4)2O2 and
Ba[(MoO2)6(IO4)2O4]·H2O have been reported the ob-
servation of the [IO4]3− anions,12,13 but both of them crystallize
in centrosymmetric (CS) structures with no second harmonic
generation (SHG) response. [I3O8]− is a kind of polyiodate(V)
formed from the condensation of three anions [IO3]−, containing
both IO3 and IO4 polyhedra. Some anions of compounds, such as
31
NaVO2(IO3)2(H2O)30 and K(VO)2O2(IO3)3 by the Mao
group. These iodates show that the stereochemically active lone
pair on the I(V) atom can be an asymmetric building unit
producing a large SHG response. In addition, NaI3O8 and some
heavy metal iodates, which are investigated by the Gautier-
Luneau group, show a wide transparency range with IR cutoffs
reaching 12 μm or longer wavelengths, thereby being a class of
promising IR NLO material.14,32,33
Bismuth(III) is a heavy metal cation containing a lone
electron pair like I(V), which in combination with the iodate
anion can lead to both a large SHG response and a wide
transparency range. However, two bismuth iodates, Bi(IO3)3
Received: September 10, 2011
Published: November 10, 2011
© 2011 American Chemical Society
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carried out with the use of the program Crystalclear,40 and face-
indexed absorption corrections were performed numerically with the
use of the program XPREP.41 The structure was solved with the direct
methods program SHELXS and refined with the least-squares program
SHELXL of the SHELXTL.PC suite of programs. The final refinement
included anisotropic displacement parameters for Bi and I atoms and a
secondary extinction correction. The program STRUCTURE TIDY42
was then employed to standardize the atomic coordinates. Additional
experimental details are given in Table 1 and selected metrical data are
and Bi(IO3)3·2H2O, have been found to be CS with no SHG
response.34,35 Recently, we and Halasyamani’s group have
independently reported the same compound, namely, BiO-
(IO3),36,37 which is synthesized by hydrothermal methods using
excess HIO3 and HNO3 as the acid mineralizer, respectively. It
displays a noncentrosymmetric (NCS) layered structure
topology, containing layers of (Bi2O2)2+ cations that are
connected to (IO3)− anions, and has a large SHG response.36,37
In the present work, we report the synthesis, characterization,
and electronic and NLO properties of a novel material in the
Bi−I−O ternary system formulated as Bi2(IO4)(IO3)3 (1).
Compound 1 has a three-dimensional (3D) framework, is the
first NCS structure with [IO4]3− anions, and produces a
moderately strong SHG response of 5 × KH2PO4 (KDP) with
an IR cutoff wavelength up to 12.3 μm.
Table 1. Crystal Data and Structure Refinements for
Bi2(IO4)(IO3)3
formula
Bi2(IO4)(IO3)3
1133.56
formula weight (g/mol)
crystal system
space group
a (Å)
orthorhombic
P212121 (19)
5.6831(11)
12.394(3)
16.849(3)
1186.8(4)
4
EXPERIMENTAL SECTION
■
b (Å)
Materials and Methods. The chemicals used in this work were
all AR grade and were purchased from commercial suppliers and used
without further purification. Microprobe elemental analyses were
performed on a Hitachi S-3500 SEM with an energy-dispersive X-ray
spectroscope (EDS). Inductive-coupled plasma atomic emission
spectrometry (ICP-AES) was performed on IRIS Intrepid II XSP
(U.S. ThermoFisher) at 22 °C and a relative humidity of 18%. Powder
X-ray diffraction patterns were recorded in the 2θ range of 5−70° with
a scan step width of 0.02° using an automated Bruker D8 X-ray
diffractometer equipped with a diffracted monochromator set for Cu
Kα (λ = 1.5418 Å) radiation. Thermogravimetric analyses (TGA) and
differential scanning calorimetric (DSC) analyses were performed
under N2 at a scan rate of 10 °C/min on a NETZSCH STA 449C
analyzer. IR spectra were recorded on a Bruker Vertex 70 V
spectrometer using the ATR technique with a ZnSe crystal in the
range of 4500−600 cm−1 (2.2−16.7 μm). The UV−vis diffuse
reflectance spectra were measured at room temperature with a Varian
Cary 5000 UV−visible-NIR spectrophotometer in the range of 2500−
250 nm (0.5−5 eV). The straightforward extrapolation method was
used to deduce the band gap and absorption edge.38 The SHG tests
were carried out on the sieved powder samples by the Kurtz and Perry
method39 with a 1064 nm Q-switch Nd:YAG laser. The sample was
ground and sieved into several distinct particle size ranges (0−50, 50−
61, 61−90, 90−105, 105−125, 125−150, 150−200, and 200−300 μm).
The KDP powders of similar particle size served as a reference to
assume the effect. All of the samples were placed in separate tubes with
two quartz glass sheets. No index-matching fluid was used in any of the
experiments.
c (Å)
V (Å3)
Z
T (K)
163(2)
Λ(Mo Kα) (Å)
ρc (g/cm3)
0.71073
6.344
μ (mm−1
)
40.089
crystal size (mm3)
data/restraints/parameters
Flack parameter
0.15 × 0.08 × 0.03
3775/0/107
−0.012(4)
0.0258, 0.0529
0.0304, 0.0546
a
R1, wR2 [I > 2sigma(I)]
R1, wR2 (all data)
a
R1 = ∑||Fo| − |Fc||/∑|Fo|, wR2 = {∑[w(Fo − Fc )2]/
2
2
∑w[(Fo)2]2}1/2
.
given in Table 2. Further information may be found in Supporting
Information.
a
Table 2. Selected Bond Lengths (Å) of Bi2(IO4)(IO3)3
Bi2(IO4)(IO3)3
Bi(1)−O(3)#1
Bi(1)−O(11)#2
Bi(1)−O(7)#2
Bi(1)−O(10)#1
Bi(1)−O(6)#2
Bi(1)−O(8)#3
Bi(1)−O(2)#2
Bi(1)−O(5)#3
Bi(2)−O(3)
Bi(2)−O(9)#3
Bi(2)−O(6)
Bi(2)−O(11)#4
Bi(2)−O(4)
2.209(6)
2.244(6)
2.329(7)
2.350(6)
2.384(5)
2.728(6)
2.793(6)
2.984(6)
2.233(6)
2.237(6)
2.340(5)
2.415(6)
2.565(6)
2.633(6)
2.680(6)
3.169(6)
3.210(6)
I(1)−O(12)#6
I(1)−O(1)#6
I(1)−O(7)
I(2)−O(13)
I(2)−O(8)
I(2)−O(10)
I(3)−O(5)#7
I(3)−O(6)
I(3)−O(11)
I(3)−O(3)
1.794(6)
1.807(6)
1.836(7)
1.803(6)
1.819(6)
1.830(6)
1.807(6)
1.884(6)
1.983(6)
2.102(6)
1.801(6)
1.811(6)
1.883(6)
Synthesis of Bi2(IO4)(IO3)3. Bi(NO3)3·5H2O (485.1 mg, 1 mmol),
HIO3 (527.7 mg, 3 mmol), HNO3 (0.5 mL, ∼5 mmol), and 2.0 mL of
deionized water were loaded into a 25 mL Teflon-lined autoclave and
subsequently sealed. The autoclave was gradually heated to 215 °C in an
oven, held for 5 d, and cooled slowly to room temperature at a rate of
10 °C/h. The final pH of the reaction system was about 0.5. Then the
yellow mother liquor was decanted from the products, which were
washed with 95% ethanol and deionized water and then air-dried.
Colorless millimetric prismatic-like crystals (Figure S1 in the Supporting
Information shows one of the crystals) were collected (425.0 mg, 75%
yield based on Bi). The product purity was confirmed by powder X-ray
diffraction analyses (see Figure S2 in the Supporting Information). EDS
analyses of Bi2(IO4)(IO3)3 provided a Bi:I ratio of 1:1.99 (approx-
imately equal to 2:4). ICP-AES elemental analyses showed a 36.67%
content of Bi, which was in good agreement with 36.87% as determined
by single crystal X-ray diffraction and EDS analyses.
I(4)−O(4)#5
I(4)−O(2)#5
I(4)−O(9)#5
Bi(2)−O(8)
Bi(2)−O(12)
Bi(2)−O(7)#5
Bi(2)−O(5)#6
a
Symmetry transformations used to generate equivalent atoms: #1 x +
1/2, −y + 3/2, −z + 1; #2 −x + 3/2, −y + 2, z −1/2; #3 x − 1/2, −y +
3/2, −z + 1; #4 −x + 1, y − 1/2, −z + 3/2; #5 −x + 2, y − 1/2, −z +
3/2; #6 −x + 2, y + 1/2, −z + 3/2; #7 −x + 1, y + 1/2, −z + 3/2; #8 −
x + 3/2, −y + 1, z + 1/2; #9 −x + 3/2, −y + 2, z + 1/2; #10 x + 1, y, z.
Single Crystal Structure Determination. Single-crystal X-ray
diffraction data were collected with the use of graphite-monochrom-
atized Mo Kα (λ = 0.71073 Å) at 163 K on a Rigaku AFC10
diffractometer equipped with a Saturn CCD detector. Crystal decay
was monitored by recollecting 50 initial frames at the end of data
collection. The collection of the intensity data was carried out with the
program Crystalclear.40 Cell refinement and data reduction were
Theoretical Computations. The electronic properties are
calculated by the plane-wave pseudopotential method43 implemented
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in the CASTEP package.44 Ultrasoft pseudopotentials45 are employed
with the 6s and 6p electrons for bismuth and the 5s and 5p electrons
for iodine. For oxygen, 1s electrons for oxygen are treated as the core
electrons. The generalized gradient approximation (GGA) using the
Perdew, Burke, and Ernzerhof (PBE) functional46 are chosen for all
the calculations. A kinetic energy cutoff of 500 eV and the Monkhorst-
Pack k-point meshes47 with a density of (4 × 2 × 1) in the Brillouin
zone of the Bi2(IO4)(IO3)3 unit cell are used. Based on the electronic
band structures, the refractive indices and SHG coefficients of the
Bi2(IO4)(IO3)3 crystal are theoretically determined. The detailed
calculation formulas are shown in ref 48.
the Supporting Information. The bond valence sums (BVS) for
the Bi1, Bi2, I1, I2, I3, and I4 atoms are 3.30, 3.04, 5.02, 4.95,
4.89, and 4.75, respectively.49 It indicates that even if the Bi and
I atoms are in different coordination environments, the
oxidation states of +3 and +5 can be assigned to Bi and I
atoms, respectively.
As shown in Figure 1, Bi2(IO4)(IO3)3 has a three-
dimensional (3D) framework structure composed of the IO3,
IO4, BiO8, and BiO9 polyhedra. The BiO8 and BiO9 polyhedra
share corners and edges to form two-dimensional Bi−O layers
parallel to the ab plane with the Bi1 and Bi2 atoms lying in
chains along the a direction (Figure 2). I1, I2, and I3 atoms,
RESULTS AND DISCUSSION
■
Synthesis. Repeated attempts have led us to find the
optimum reaction conditions as indicated in Experimental
Section. In addition, the replacements of HIO3 with I2O5 or
H5IO6 and of Bi(NO3)3·5H2O with Bi2O3 as starting materials
also generated the target material. Some blue-black blocks of
I2(s) were observed as a byproduct, which was probably from
the reduction of excess HIO3 by water. Subsequently, the I2
solids were removed by washing with ethanol.
Structure Description. Bi2(IO4)(IO3)3 crystallizes in a
new structure (Figure 1) in noncentrosymmetric (NCS) space
Figure 2. Layers composed by the BiO8 and BiO9 polyhedra parallel to
the ab plane viewed down the a-axis.
which connect to the Bi atoms by bridging oxygen atoms, are
attached to these layers, while I4 atoms further join these layers
together by bridging oxygen atoms to form the 3D framework.
As for the IO3 and IO4 groups themselves, they are all
completely isolated from each other without any common O
atoms. Two compounds of iodate Ag4(UO2)4(IO3)2(IO4)2O2
and Ba[(MoO2)6(IO4)2O4]·H2O contain isolated [IO4]3‑
anions, but they both crystallize in centrosymmetric struc-
tures.12,13 Other compounds containing both IO3 and IO4
polyhedra include NaI3O8, α-Cs2(IO3)(I3O8), β-Cs2(IO3)-
(I3O8) and Rb2(IO3)(I3O8)(HIO3)2(H2O). However, in all
these compounds, the IO3 and IO4 groups are connected to
form [I3O8]− anions.11,14−16 Bi2(IO4)(IO3)3 is the first NCS
structure that contains [IO3]− and [IO4]3− anions.
Figure 1. View of crystal structure of Bi2(IO4)(IO3)3 down the a
direction.
group P212121 (No. 19) of the orthorhombic system. The
asymmetric unit contains two crystallographically independent
Bi atoms, four independent I atoms, and thirteen independent
O atoms. Figure 1 shows that I1, I2, and I4 are coordinated to a
trigonal pyramid of three O atoms with the I−O distances
ranging from 1.794(6) to 1.883(6) Å, which are comparable to
those of Bi(IO3)3 (1.790(8)−1.828(8) Å)34 and some other
iodates containing IO3 groups (1.777(6)−1.930(5) Å).11
Furthermore, I3 is coordinated to four O atoms in a ‘seesaw’
environment with the I−O distances of 1.807(6)−2.102(6) Å,
which are in agreement with those of 1.818(6)−2.054(6) Å in
Ag4(UO2)4(IO3)2(IO4)2O212 and Ba[(MoO2)6(IO4)2O4]·H2O.
The coordination polyhedra of Bi1 and Bi2 cations are irregular
with coordination numbers of 8 and 9 and Bi−O distances in
the range of 2.209(6)−3.210(6) Å. These Bi−O distances are
close to those of 2.387(7)−2.996(9) Å in Bi(IO3)3.34 Selected
bond distances are presented in Table 2, and the coordination
environments of I1, I2, I3, and I4 are showed in Figure S3 in
Thermal Studies. The TGA-DSC curves, as shown in
Figure S4 in the Supporting Information, indicate that
Bi2(IO4)(IO3)3 is thermally stable up to about 400 °C and
displays three steps of weight loss, which are in agreement with
the three endothermic peaks at 534, 570, and 845 °C,
respectively. At 550 and 650 °C, the products of thermal
37
decomposition should be BiIO4 and α-Bi5O7I (JCPDS No.
01-071-3024), as confirmed by powder XRD studies (see
Figures S5 and S6 in the Supporting Information). The
experimental weight losses are in good agreement with
calculated values (Supporting Information Figure S4). The
residuals at 900 °C may be Bi2O3 by calculation, but collection
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and analysis were difficult because they were in small amount
and deposited on the walls of the Al2O3 crucible.
for ground Bi2(IO4)(IO3)3 crystals. For large particle sizes, the
second harmonic intensity is independent of particle size. The
tendency of the curve indicates that Bi2(IO4)(IO3)3 belongs to
the type 1 phase-matching class according to the rules proposed
by Kurtz and Perry.39 Comparisons of the second harmonic
signals produced by Bi2(IO4)(IO3)3 and KDP in the same
particle range (150 to 200 μm) reveal that Bi2(IO4)(IO3)3
exhibits a moderately large SHG response of about 5 × KDP.
The moderately large SHG efficiency is consistent with the
electronic structure calculation.
IR and UV−vis Diffuse Reflectance Spectra. IR spectra
show five main peaks: 810 (νI−O, w), 748 (νI−O, s), 725 (νI−O, s),
692 (νI−O, s), 662 (νI−O, s) cm−1, which are in good agreement
with the I−O stretching vibrations in the regions of 600−
840 cm−1.16,33 It indicates that Bi2(IO4)(IO3)3 is transparent in the
range of 4500−813 cm−1 (2.2−12.3 μm) with IR cutoff
wavelengths moving into the far-IR region (Figure S7 in the
Supporting Information).
Electronic Structure Calculation. The electronic band
structures of Bi2(IO4)(IO3)3 are shown in Supporting Information
Figure S8, along the lines of high symmetry points in the Brillouin
zone. It is shown that Bi2(IO4)(IO3)3 is a direct gap crystal with
the band gap of 3.17 eV, which is very close to the experimental
value of 3.3 eV. The partial density of state (PDOS) projected on
the constitutional atoms of the Bi2(IO4)(IO3)3 crystal is shown in
Supporting Information Figure S9. Clearly, the valence band (VB)
lower than −10 eV mainly consists of 2s orbitals for oxygen and 5s
and 5p orbitals for iodine. The upper part of the VB from −10 to
0 eV is mainly composed of 2p orbitals of oxygen, 6s and 6p
orbitals of bismuth and 5p orbitals of iodine, but the very top
mostly consists of O 2p orbitals. There is significant hybridization
between O 2p orbitals and I 5p orbitals, as well as Bi 6s and 6p
orbitals. The bottom of the conduction band (CB) is composed of
the orbitals of all atoms, and the p orbitals of I and Bi determine
the CB minimum of Bi2(IO4)(IO3)3.
UV−vis Diffuse Reflectance Spectra shown in Figure 3
indicate that Bi2(IO4)(IO3)3 is a wide gap semiconductor with
On the basis of the electronic band structure, the linear and
nonlinear optical properties of Bi2(IO4)(IO3)3 have been
calculated. It is shown that the linear refractive indices are nx =
2.330, ny = 2.526, and nz = 2.414 at the radiation wavelength of
1064 nm. Clearly, the birefringence is quite large with Δn = 0.196,
so this crystal is relatively easy to achieve the phase-matching
conditions for the SHG light output. Meanwhile, the calculated
SHG coefficient is d36 = −1.58 pm/V, which is very close to our
experimental value of 5 times of KDP (d36 = 0.39 pm/V).
Therefore, we conclude that Bi2(IO4)(IO3)3 is a promising NLO
crystal, which can be applied in the IR region.
From the viewpoint of structural features, the strong
anisotropic response (or birefringence) to the incident
radiation is due to the large distortion of the BiO8 and BiO9
polyhedra and the presence of the lone-pair electrons on I
atoms that occupy vertexes of the I−O triangular pyramids or
quadrilateral pyramids. However, the spatial arrangement of
those microscopic units is not regular, so the microscopic
second-order susceptibilities of a group partly counteract those
of another group, resulting in the decrease of the overall SHG
effects. It is expected that if those active microscopic units
could be aligned, the capability of this crystal to produce the
larger nonlinear optical light output would be significantly
improved. These structural understandings can give us some
ideas to design NLO crystals with enhanced NLO effects.
Figure 3. UV−vis diffuse reflectance spectra for Bi2(IO4)(IO3)3 with
band gap of 3.3 eV.
an absorption edge of 376 nm and optical band gap of 3.3 eV.
Band gaps have great influence on the laser damage threshold
of IR NLO materials. With a large band gap, which is consistent
with the crystal colorlessness, Bi2(IO4)(IO3)3 should have a
high laser damage threshold.10,50
Second Harmonic Generation (SHG) Properties. Figure 4
shows the curves of the SHG signal intensity versus particle size
CONCLUSION
■
In summary, a promising IR NLO material, Bi2(IO4)(IO3)3, has
been prepared. It crystallizes in an acentric space group and displays
a 3D framework composed of the IO3, IO4, BiO8 and BiO9 groups.
Interestingly, it is the first time that the [IO4]3− anion occurs in a
noncentrosymmetric (NCS) compound of iodate. Moreover,
the new compound is thermally stable, has a transparency range
up to the beginning of the far-IR region, and displays intense
SHG signals. On the basis of the SHG measurements on
powders and theoretical calculations, Bi2(IO4)(IO3)3 readily
Figure 4. Phase-matching curve (Type 1) for Bi2(IO4)(IO3)3. The
curve is to guide the eye and is not a fit to the data.
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(21) Abrahams, S. C.; Bernstein, J. L.; Nassau, K. J. Solid State Chem.
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achieves the type 1 phase-matching conditions with a moderately
large SHG response of approximately 5 × KDP. These findings
have led us to conclude that this compound has potential
applications as a quadratic NLO material. Further research on
Bi2(IO4)(IO3)3 is in progress, which includes growing larger-size
crystals and evaluating their optical properties such as refractive
index, the Sellmeier equations, second-order NLO coefficients
and the laser damage threshold.
(22) Abrahams, S. C.; Bernstein, J. L. Solid State Commun. 1978, 27,
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ASSOCIATED CONTENT
* Supporting Information
■
S
X-ray crystallographic file in CIF format, photograph of single
crystal, simulated and experimental XRD patterns, picture of
IO3 and IO4 polyhedra, TGA and DSC curves, XRD studies of
the thermal decomposition for the compound, IR spectra,
electronic band structure, and partial density of states of
Bi2(IO4)(IO3)3 (PDF). This material is available free of charge
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AUTHOR INFORMATION
Corresponding Author
*E-mail: hu@mail.ipc.ac.cn.
■
ACKNOWLEDGMENTS
We thank Prof. Xiaotai Wang for helpful discussions.
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