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Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX

Syntheses, Structures, and Properties of Non-Centrosymmetric Quaternary Tellurates BiMTeO6 (M = Al, Ga) Fenghua Ding,†,‡ Matthew L. Nisbet,‡ Hongwei Yu,‡ Weiguo Zhang,§ Liyuan Chai,† P. Shiv Halasyamani,§ and Kenneth R. Poeppelmeier*,‡ †

School of Metallurgy and Environment, Central South University, Changsha 410083, China Department of Chemistry, Northwestern University, Evanston, Illinois 60208-3113, United States § Department of Chemistry, University of Houston, Houston, Texas 77204, United States Downloaded via UNIV OF CALIFORNIA SANTA BARBARA on June 18, 2018 at 03:17:36 (UTC). See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.



S Supporting Information *

ABSTRACT: Single crystals of two new metal tellurates BiMTeO6 (M = Al, Ga) with a honeycomb layered structure were obtained by the molten flux method and characterized. The BiMTeO6 compounds both crystallize into a noncentrosymmetric trigonal space group of P312 (no. 149) with cell parameters of a = 5.0667(8) Å, c = 4.9920(16) Å and a = 5.107(3) Å, c = 4.932(6) Å, respectively. The noncentrosymmetry of BiAlTeO6 and BiGaTeO6 originates from the packing order of the octahedra. In these two structures, TeO6 octahedra and MO6 octahedra share edges and form a honeycomb open-framework with [TeMO6]∞ layers. The layers of [MTeO6]∞ and [BiO6]∞ alternate and are connected along the c-axis by corner-sharing oxygen atoms to form the threedimensional framework. The chiral compound BiGaTeO6 exhibits a powder second harmonic generation (SHG) response of ∼0.2 times that of potassium dihydrogen phosphate (KDP) and an absorption edge of 355 nm.



INTRODUCTION Non-centrosymmetric (NCS) materials possess important physical properties; some exhibit SHG, ferroelectricity, pyroelectricity, piezoelectricity, multiferroicity,1−5 or rotate a plane of polarized light, a phenomenon known as optical activity (optical rotation).6,7 Although many NCS materials have been discovered, developing methods for the rational design of functional inorganic compounds remains a challenge. In many cases, the macroscopic non-centrosymmetry is a manifestation of the acentric coordination environments of cations such as pconjugated planar groups (e.g., BO33−),8−13 rigid tetrahedral groups (e.g., PO43−, BO45−, BeO44−),12,14−17 octahedral d0 early transition metals (TM) (e.g., Nb5+, V5+, Mo6+),18−20 d10 late transition metals (e.g., Zn2+, Cd2+),21−24 and main group atoms with lone pairs (e.g., Pb2+, Bi3+, Se4+, Te4+, I5+).5,25−29 Even though inclusion or combination of these NCS units does not guarantee an NCS structure, one can arrange individual units into an overall NCS crystal structure by consideration and manipulation of the interactions of locally acentric units with their surrounding environment.30−36 Going beyond the local acentric environment of the building units and controllable arrangement strategies listed above, PbSb2O6-type compounds exhibit non-centrosymmetry due to the stacking order of cations in a honeycomb lattice. PbSb2O6 was originally assigned to the chiral NCS space group P312 by Magneli37 in 1941 using single-crystal diffraction but was later reassigned by Hill38 in 1987 to P3̅1m, a centrosymmetric (CS) supergroup of P312. The PbSb2O6 structure contains sheets of © XXXX American Chemical Society

edge-sharing SbO6 octahedra oriented perpendicular to the caxis. Interestingly, quaternary tellurates adopt this structure type (general formula ABTeO6) through substitution for Sb5+ by B and Te6+ cations to create distinct sites previously occupied by equivalent Sb atoms. The exploratory synthesis of compounds with the formula A2+B4+TeO6 has produced NCS compounds in the space group P312 (MnGeTeO 6 ,39 CdGeTeO6,39 PbGeTeO6,39 SrGeTeO6,40 BaGeTeO641) with ordered B-site cations in an octahedral environment. Ordered Te and Ge atoms within the layer break inversion symmetry for the chiral P312 structure, while for PbSb2O6 (P3̅1m), equivalent Sb atoms are related by inversion. SrMnTeO6 and PbMnTeO6, other NCS compounds in the A2+B4+TeO6 family, have been reported in the space group P6̅2m31 and display disordered B-cations in an acentric trigonal prismatic coordination environment. Related CS phases with the formula A3+B3+TeO6 incorporating trivalent metals on the A site were reported in the space groups P3̅ (LnCrTeO6 (Ln = Y, La, Tb, Er))42 and P3̅1c (BiMTeO6 (M = Cr, Fe)),43 which display partially ordered or disordered transition metal B cations arranged in alternating Te−B−Te stacks along the c-direction as opposed to the Te−Te−Te and B−B−B stacks observed for NCS ABTeO6 structures. Additionally, the compound BiMnTeO6 formed with fully ordered B cations but crystallized in the lower symmetry monoclinic space group P21/c as a Received: April 19, 2018

A

DOI: 10.1021/acs.inorgchem.8b01087 Inorg. Chem. XXXX, XXX, XXX−XXX

Article

Inorganic Chemistry result of the Jahn−Teller distortion of the trivalent Mn3+ on the B site.38−40 These results suggest that the electronic effects of B-site cations play a critical role in the structure type of ABTeO6. If the B-site is occupied by a main group cation, the B-site and Te6+ cations are more likely to order in an octahedral environment and crystallize into chiral structures (Table 1).

ranges for the test. Ground KDP powder was used as a reference and sieved into the same size ranges. The intensities of the frequencydoubled output emitted from the samples were detected by a photomultiplier tube. Synthesis. The polycrystalline powder of BiGaTeO6 was prepared via the solid state reaction method with stoichiometric amounts of 0.562 g of Ga2O3, 1.398 g of Bi2O3, and 1.053 g of TeO3. Amorphous TeO3 was synthesized preliminarily by calcining H2TeO4·2H2O at 400 °C for 12 h in an air atmosphere. The reagents were ground together in an agate mortar and pestle and pressed into a pellet, which was placed in a platinum crucible, heated to 700 °C at a rate of 10 °C/min, and held at this temperature for 40 h, with several intermittent grindings. The furnace was then quenched to room temperature naturally. White powder was obtained, and the purity was then confirmed by powder X-ray diffraction. Attempts to prepare single phase BiAlTeO6 via the solid state reaction method with stoichiometric amounts of Al2O3, Bi2O3, and TeO3 (or TeO2) were unsuccessful. X-ray powder diffraction showed that the resulting mixture consisted of Bi2TeO5, as well as Bi2Te2O7, aside from BiAlTeO6 (Figure S1). Colorless crystals of BiGaTeO6 were successfully obtained by the molten flux method. The TeO2−Na2CO3 flux system, with a mole ratio of 1:4:1:1 Na2CO3/TeO2/Bi2O3/Ga2O3, was placed in a platinum crucible, heated to 750 °C, and then held at this temperature for 10 h to melt completely. The furnace was cooled to 400 °C at a rate of 0.1 °C/min and then quenched to room temperature naturally. Colorless crystals of BiAlTeO6 were obtained from a mixture with a mole ratio of 1:4:1 Na2CO3/TeO2/Bi2O3. The mixture was placed in an aluminum crucible, heated to 700 °C, and then held at this temperature for 5 h to melt completely. The furnace was cooled to 400 °C at a rate of 0.1 °C/min and then quenched to room temperature naturally. Powder X-ray Diffraction (PXRD). Powder XRD measurements on BiMTeO6 (M = Al, Ga) were performed at room temperature on a Rigaku Ultima diffractometer with graphite monochromatized Cu Kα (λ = 1.5418 Å) radiation. The measured powder XRD patterns of BiGaTeO6 were in agreement with the simulated patterns from singlecrystal X-ray diffraction studies (Figure S2). Single-Crystal X-ray Diffraction. Colorless and transparent block crystals with dimensions of 0.148 × 0.104 × 0.057 mm for BiAlTeO6 and 0.117 × 0.056 × 0.043 mm for BiGaTeO6 were chosen for structure determination (Table 2). Single-crystal XRD data were obtained at 100 K with a Bruker Kappa APEX 2 CCD diffractometer with monochromated Mo Kα radiation (λ = 0.7107 Å). The crystalto-detector distances were set as 40 mm and 50 mm, respectively. The SAINT program was used for data reduction and integration.47 The structures were established by direct methods and refined through full-matrix least-squares fitting on F2 using SHELX-97.48 All atoms were refined using full-matrix least-squares techniques, and final leastsquares refinement was on F02 with data of F02 ≥ 2σ(F02). Numerical absorption corrections were carried out using the SADABS program for area detector. The structures were solved with the use of Shel-XS to determine the atomic coordinates of the metallic cations. The structures were examined for possible missing symmetry elements with PLATON, and no additional symmetry was found.49 Other crystallographic data are reported as CIFs in the Accession Codes and in the Supporting Information.

Table 1. Summary of the PbSb2O6-Type Tellurates when the B-Site Cation Is a Transition or Main Group Element type of B-site cation transition cation

main group cation

PbSb2O6-type tellurate (ABTeO6) YCrTeO6,42 TbCrTeO6,42 ErCrTeO642 BiCrTeO6,43 BiFeTeO643 BiMnTeO638−40 MnGeTeO6,39 CdGeTeO6,39 PbGeTeO6,39 SrGeTeO6,40 BaGeTeO641

space group P3̅a P3̅1ca P21/ca P312b

a

Centrosymmetric space group. bNon-centrosymmetric space group.

Here, we report the synthesis and characterization of two new quaternary NCS tellurates that incorporate trivalent A and B cations in the honeycomb PbSb2O6 structure. The design of new NCS tellurates with Bi3+ cations was successfully attempted by incorporating main group Al3+ and Ga3+ cations without a Jahn−Teller distortion on the B site. Interestingly, the title compounds are extended inorganic solids that form chiral crystal structures despite being composed of achiral objects.44 Single crystals were obtained by the molten flux method, and the structures were determined by single-crystal X-ray diffraction. The compound BiGaTeO6 was obtained as a single phase and characterized using UV−Vis−NIR absorption spectroscopy, Fourier transform infrared spectroscopy, and Kurtz-Perry second-harmonic generation measurements.



EXPERIMENTAL SECTION

Materials and Instruments. Bismuth oxide (Bi2O3, 99.9%), aluminum oxide (Al2O3, 99.9%), gallium oxide (Ga2O3, 99.9%), tellurium dioxide (TeO2, 99.9%), tellurium acid (H2TeO4·2H2O, 99.6%), and sodium carbonate (Na2CO3, 99.0%) were used as received from Sigma-Aldrich. The Fourier transform infrared spectroscopy (FTIR) spectra in the 600−4000 cm−1 range were recorded on a Bruker 37 Tensor FTIR spectrometer at room temperature. Surface imaging and composition analysis by energy dispersive spectroscopy (EDS) on as-grown crystals was performed using a Hitachi S8030 scanning electron microscope (SEM) equipped with a PGT energy dispersive X-ray analyzer with an accelerating voltage of 15 kV and a 100 s accumulation time for data acquisition. UV−Vis diffuse reflectance spectra were collected with a UV-3600 Shimadzu UV−Vis−NIR spectrophotometer over the spectral range of 200−1500 nm at room temperature. Barium sulfate (BaSO4) was used as a standard sample for the baseline correction. The sample was thoroughly mixed with BaSO4, and this mixture was used for UV−Vis measurements. Reflectance spectra were converted to absorbance using the Kubelka−Munk equation.45,46 The thermogravimetric analysis (TGA) and differential thermal analysis (DTA) were carried out with a NETZSCH-Proteus-61 analyzer instrument. Crystal samples were added into an aluminum crucible and heated from room temperature to 900 °C at a rate of 10 K/min and then cooled to room temperature at the same rate under flowing air with a flow rate of 25 mL/min. The SHG measurements of polycrystalline samples were performed with a Nd:YAG laser (λ = 1064 nm) as the incident light source. Samples of BiGaTeO6 were ground and sieved into seven distinct size



RESULTS AND DISCUSSION Structure and Description. The title compounds BiAlTeO6 and BiGaTeO6 both crystallize in a non-centrosymmetric trigonal space group, P312 (no. 149), with the cell parameters of a = 5.0667(8) Å, c = 4.9920(16) Å and a = 5.107(3) Å, c = 4.932(6) Å, respectively. Atomic coordinates (×104) with equivalent isotropic displacement parameters (× 103 Å2), selected bond lengths (Å), and angles (°) for BiMTeO6 (M = Al, Ga) are listed in Tables S1 and S2, respectively. B

DOI: 10.1021/acs.inorgchem.8b01087 Inorg. Chem. XXXX, XXX, XXX−XXX

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trigonal planar. With respect to the Te6+ and Al3+ cationcentered octahedra, the angles O−Te−O range from 80.1(19)° to 169.3(16)° with six nearly equivalent Te−O bond lengths of 1.923(52) Å, while the O−Al−O angle ranges from 80.8(19)° to 169.7(74)° with uniform Al−O bond lengths of 1.909(52)−1.909(53) Å. As compared to PbSb2O6, the SbO6 octahedra feature nearly the same Sb−O bond length of 1.988(71) Å.38 The Te−Al distance is 2.925(5)−2.926(3) Å in BiAlTeO6, and the Te−Ga distance is 2.948(17)−2.949(12) Å in BiGaTeO6. By comparison, the Sb−Sb distances are 3.057(6)−3.058(4) Å in PbSb2O6. The net dipole moment for TeO6 and GaO6 octahedra were calculated to be 0.015 and 0.010 D (D = Debyes), respectively, using a simple bond−valence approach.51,52 The bond valence sums for BiAlTeO6 and BiGaTeO6 are calculated using the formula

Table 2. Crystal Data and Structure Refinement for BiMTeO6 (M = Al, Ga) empirical formula formula weight temperature wavelength crystal system space group unit cell dimensions volume Z density (calculated) absorption coefficient F(000) crystal size index ranges independent reflections refinement method data/restraints/ parameters goodness-of-fit on F2 flack factor final R indices [I > 2σ(I)]a R indices (all data) largest diff. peak and hole

BiAlTeO6 379.56 107(2) K 0.71073 Å trigonal P312 a = 5.0667(8) Å

BiGaTeO6 502.30 107(2) K 0.71073 Å trigonal P312 a = 5.107(3) Å

c = 4.9920(16) Å 110.98(5) Å3 1 5.679 g/cm3

c = 4.932(6) Å 111.40(19) Å3 1 7.487 g/cm3

46.153 mm−1

51.845 mm−1

156 0.148 × 0.104 × 0.057 mm3 −7 ≤ h ≤ 7, −7 ≤ k ≤ 7, 6≤l≤6 214 [R(int) = 0.0312]

214 0.117 × 0.056 × 0.043 mm3 −6 ≤ h ≤ 6, −6 ≤ k ≤ 6, −6 ≤ l ≤ 6 189 [R(int) = 0.0267]

full-matrix least-squares on F2 214/0/17

full-matrix least-squares on F2 189/12/18

1.084

1.243

−0.012(12) R1 = 0.0124, wR2 = 0.0321 R1 = 0.0124, wR2 = 0.0321 0.958 and −1.020 eÅ−3

0.494(12) R1 = 0.0101, wR2 = 0.0233

Vi =

∑ Sij = ∑ exp{(r0 − rij)/B} j

j

where Sij is the bond valence associated with bond length rij, and r0 and B (usually 0.37) are empirically determined parameters.53 The results of the bond valence sum calculations are 2.78, 2.99, 5.88, and −1.94 for the Bi, Al, Te, and O atoms, respectively, which indicates that they are in the expected states of +3, +3, +6, and −2, respectively. The bond valence calculation values of 3.01, 3.26, 5.92, and −1.93 for the Bi, Ga, Te, and O atoms, respectively, are also in agreement with the expected values. The EDS analysis (Figures S3 and S4) gave an atomic ratio for Bi/Al/Te of 1:1:1 for the compound BiAlTeO6 and a ratio for Bi/Ga/Te of 1:1:1 for the compound BiGaTeO6, which were in good agreement of the formula sum deduced by single-crystal XRD analysis. Chirality Progression from the Parent PbSb 2 O6 Structure. We will examine the group−subgroup relationships between the parent PbSb2O6 structure (P3̅1m) and related NCS and CS subgroups to understand the origin of chirality in the NCS P312 structure adopted by BiAlTeO6 and BiGaTeO6. In the high symmetry CS P3̅1m parent compound PbSb2O6, equivalent Sb atoms are related across an inversion center within the Sb layer (Figure 2) and Sb−Sb stacks form along the c-direction by translational symmetry. Equivalence of the Sb atoms is broken through substitution of fully or partially ordered B3+ and Te6+ cations in the A3+B3+TeO6 family; however, cation ordering along the c-axis dictates whether the structure is CS or NCS. When transition metal B3+ cations (Cr, Fe, Mn) are paired with A3+ cations, B−Te−B and Te−B−Te stacks form along the c-direction and the unit cell is doubled along the same direction (c′ = 2c). Alternating stacks are related to each other through inversion centers between the B/ Te layers, and the resulting structure can be assigned to P3̅1c (BiCrTeO6, partially ordered) or P3̅ (YCrTeO6, ordered), both of which are maximal subgroups of P3̅1m54 (Figure 2(b, c)). Further, in the case of BiMnTeO6, which displays the same stacking order as YCrTeO6, the first-order Jahn−Teller distortion of Mn3+ results in the loss of 3-fold rotational symmetry and the resulting symmetry is lowered to P21/c (Figure 2(d)). Within the A3+B3+TeO6 family, B−B and Te− Te stacking orders can be found along the c-direction only when a main group B3+ cation is chosen, and the resulting structure is classified in the NCS subgroup P312 (Figure 2(e)). The difference in stacking order can be explained by examining the coordination sphere of Te6+ in each structure. In the CS P3̅ structure of YCrTeO6, Te−O bond lengths of 2.090 Å are

R1 = 0.0101, wR2 = 0.0233 0.713 and −0.686 eÅ−3

R1 = ∑||F0| − |Fc||/∑|F0| and wR2 = [∑w(F02 − Fc2)2/∑wF04]1/2 for F02 > 2σ(F02).

a

BiAlTeO6 and BiGaTeO6 are isostructural and display very similar 3D anionic frameworks. Therefore, only the structure of BiAlTeO6 is discussed in detail as a representative. All of the Bi, Te, and Al atoms are octahedrally coordinated. In the abplane, TeO6 octahedra and AlO6 octahedra share edges and form a honeycomb-like open-framework [AlTeO6]∞ layer, similar to the [Sb2O6]∞ layer in the PbSb2O6. [AlTeO6]∞ can be viewed as an aliovalent substitution for two Sb5+ cations by Al3+ and Te6+ and Bi3+ on the Pb2+ site (Figure 1(a−d)). The BiO6 octahedra show a layer arrangement even though they do not connect with each other. The layers of [AlTeO6]∞ and [BiO6]∞ alternate and connect along the c-axis via cornersharing oxygen atoms to form the three-dimensional framework (Figure 1(e, f)). The isolated BiO6 octahedra are positioned above and below the vacant sites in the adjacent [AlTeO6]∞ layers. The TeO6 and AlO6 octahedra belong to the point group D3, while BiO6 octahedra have the symmetry D3d. In the Bi3+-centered octahedra, the Bi3+ cation remains at the center with six uniform bond lengths of 2.375(52)− 2.376(52) Å and O−Bi−O angles between 87.2(13)° and 179.5(12)°. The uniform Bi−O bond lengths indicate that the 6s2 lone pair of the Bi3+ cation is non-stereoactive, similar to other Bi3+-containing layered oxides.43,50 Oxygen atoms are positioned on the 6i Wyckoff site with C1 symmetry. Each oxygen atom is coordinated by one Te atom, one Al atom, and one Bi atom in a geometry that is slightly distorted from C

DOI: 10.1021/acs.inorgchem.8b01087 Inorg. Chem. XXXX, XXX, XXX−XXX

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Figure 1. Ball-and-stick representation and projection of the structure of PbSb2O6 and BiAlTeO6 (a−d), the honeycomb-like [AlTeO6]∞ layer (e), and the three-dimensional framework (f).

Figure 2. Ball-and-stick representation and space group of PbSb2O6 (a) and BiCrTeO6 (b), YCrTeO6 (c), BiMnTeO6 (d), and BiGaTeO6 (e).

the c-direction (3̅ → 3) and degrade m (equals to 2̅) symmetry into the 2-fold axis only in the [210] direction (2̅ → 2), compared to the structure of the parent compound. In this way, the parent CS structure transfers into the chiral P312 structure (see Figure 3). IR Spectroscopy. The IR spectra for BiAlTeO6 and BiGaTeO6 are shown in Figure S5. The strong absorption peaks around 596 and 636 cm−1 can be assigned to the Al−O and Ga−O stretching modes in an octahedral environment, respectively.55,56 The weak peaks around 777 and 704 cm−1 are due to the symmetrical vibrations of Te−O bonds in BiAlTeO6 and BiGaTeO6, respectively. Bi2TeO5 and Bi2Te2O7 are present as secondary phases in the sample containing

observed, compared to the Te−O distance of 1.922 (1.924) Å in the NCS P312 structure for BiGaTeO6 (BiAlTeO6). The differences in Te−O bond lengths indicate that Te is underbonded in the CS structure, which favors an alternating B−Te−B stacking arrangement rather than the B−B/Te−Te stacking seen in the P312 structure. As a consequence of the ordering of B and Te and the B−B/Te−Te stacking order, the NCS P312 structure of the title compounds lacks inversion symmetry between the B and Te sites, where Sb atoms sit in the parent P3̅1m structure, as well as inversion between layers, as also observed in the P3̅ structure. In other words, the structures of the title compounds preserve only the 3-fold axis along the c-direction while removing the inversion symmetry in D

DOI: 10.1021/acs.inorgchem.8b01087 Inorg. Chem. XXXX, XXX, XXX−XXX

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Figure 3. The BiAlTeO6 structure is enantiomorphic (D3) despite the lack of a local chiral center. Inversion symmetry is broken within the structure based on cation ordering of Al and Te within each honeycomb layer. Figure 5. Powder SHG measurement of polycrystalline BiGaTeO6 at the fundamental wavelength of 1064 nm. Note the curves are drawn to guide the eye and are not a fit to the data.

BiAlTeO6 as the major phase, but peaks from these phases could not be distinguished in the FTIR spectrum of BiAlTeO6. UV−Vis Diffuse Reflectance Spectroscopy. The UV− Vis−IR diffuse-reflectance spectra for BiGaTeO6 is shown in Figure S6. Absorption (K/S) data were calculated from the following Kubelka−Munk function: F = (1 − R)2/2R = K/S, where R represents the reflectance, K the absorption, and S the scattering. The minima in the second-derivative curves of the Kubelka−Munk function are taken as the maxima of the absorption bands. The absorption edge of BiGaTeO6 is about 355 nm (i.e., 3.49 eV), indicating that BiGaTeO6 is a promising NLO crystal in the visible to near UV range. Thermal Analysis. The TGA curve of BiGaTeO6 powder shows its weight loss, which begins at 806 °C. On the DTA curve, there are two exothermic peaks around 834 and 877 °C (Figure 4). The powder X-ray diffraction pattern of the



CONCLUSION We have successfully explored, synthesized, and characterized two new tellurate compounds, BiMTeO6 (M = Al, Ga) by aliovalent substitution for PbSb2O6. They adopt the same anionic open frameworks based on BiO6, TeO6, and MO6 octahedra. The last two kinds of octahedra form a honeycomb [TeMO6]∞ layers by sharing edges. The layers of [MTeO6]∞ and [BiO6]∞ alternate and connect to each other along the caxis by corner-sharing oxygen atoms to form the threedimensional structure. The non-centrosymmetry of BiTeAlO6 and BiTeGaO6 originates from the packing order of the octahedra. Their single crystals were grown by the molten flux method by using a TeO2−Na2CO3 flux system. The pure phase of BiGaTeO6 was obtained by a solid state reaction method. Second harmonic generation confirms the non-centrosymmetric character. The absorption edge is about 355 nm. Its SHG intensity is ∼0.2 × KDP and can be phase-matchable. Extended work on other non-centrosymmetric PbSb2O6-type compounds is worth additional study.



ASSOCIATED CONTENT

* Supporting Information S

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.8b01087. Atomic coordinates, equivalent isotropic displacement parameters, and the bond valence sums of each atom; selected bond distances and angles; experimental and calculated XRD patterns; EDS analysis; IR spectroscopy; and UV−Vis diffuse reflectance spectroscopy (PDF)

Figure 4. TG/DTA curves for BiGaTeO6 compound.

remaining sample after TG/DTA is identified as Bi2Te2O7, Ga2O3, and some unknown phases by powder X-ray diffraction (Figure S7). Those indicate that BiGaTeO6 melts incongruently. Therefore, the molten flux method should be used to grow single crystals of BiGaTeO6. Second Harmonic Generation. The BiGaTeO6 compound crystallizes into an NCS trigonal space group of P312, which can exhibit SHG behavior. Powder SHG measurements were carried out with an incident laser of 1064 nm. The SHG intensity is about ∼0.2 times that of KDP at the same particle size range (Figure 5). The results show that BiGaTeO6 is typeI phase-matchable.57 This is direct evidence for the lack of an inversion center in the lattice. The weak SHG response may be attributed to the slight distortion of TeO 6 and GaO 6 octahedra.58

Accession Codes

CCDC 1826279−1826280 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.



AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

Fenghua Ding: 0000-0002-9529-3023 E

DOI: 10.1021/acs.inorgchem.8b01087 Inorg. Chem. XXXX, XXX, XXX−XXX

Article

Inorganic Chemistry

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Hongwei Yu: 0000-0002-5607-0628 P. Shiv Halasyamani: 0000-0003-1787-1040 Kenneth R. Poeppelmeier: 0000-0003-1655-9127 Notes

The authors declare no competing financial interest.



ACKNOWLEDGMENTS This work was supported by funding from the National Science Foundation (DMR-1608218). The single-crystal X-ray data and FT-IR measurements were acquired at Northwestern University′s Integrated Molecular Structure Education and Research Center (IMSERC) at Northwestern University, which is supported by grants from NSF-NSEC, NSFMRSEC, the KECK Foundation, the State of Illinois, and Northwestern University. This work made use of the J. B. Cohen X-ray Diffraction Facility supported by the MRSEC program of the National Science Foundation (DMR-1720139) at the Materials Research Center of Northwestern University. H.Y., W.G., and P.S.H. thank the Welch Foundation (E-1457) and the NSF (DMR-1503573) for support.



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DOI: 10.1021/acs.inorgchem.8b01087 Inorg. Chem. XXXX, XXX, XXX−XXX

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DOI: 10.1021/acs.inorgchem.8b01087 Inorg. Chem. XXXX, XXX, XXX−XXX