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Jul 25, 2017 - ABSTRACT: A novel lithium-rich transition metal selenite, Li13Mn(SeO3)8, that is composed of a Jahn−Teller distortive cation, Mn3+, i...
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Li13Mn(SeO3)8: Lithium-Rich Transition Metal Selenite Containing Jahn−Teller Distortive Cations Hongil Jo,† Seung Yoon Song,† Eunjeong Cho,† Jongho So,† Suheon Lee,‡ Kwang Yong Choi,‡ and Kang Min Ok*,† †

Department of Chemistry and ‡Department of Physics, Chung-Ang University, 84 Heukseok-ro, Dongjak-gu, Seoul 06974, Republic of Korea S Supporting Information *

ABSTRACT: A novel lithium-rich transition metal selenite, Li13Mn(SeO3)8, that is composed of a Jahn−Teller distortive cation, Mn3+, in the high spin d4 state, and a second-order Jahn−Teller (SOJT) distortive lone pair cation, Se4+, has been synthesized via hydrothermal and high temperature solid state reactions. The selenite is classified as a molecular compound consisting of MnO6 octahedra, SeO3 trigonal pyramids, and Li+ cations. Considering the Li−O interactions, the structure of Li13Mn(SeO3)8 may be described as a pseudo-three-dimensional framework as well. The title compound is thermally stable up to 500 °C and starts decomposing above the temperature attributable to the volatilization of SeO2. While the MnO6 octahedra in Li13Mn(SeO3)8 exhibit six identical Mn−O bond distances at room temperature due to the dynamic Jahn−Teller effect, a clear elongation of two Mn−O bonds along a specific direction is observed at 100 K. A series of isostructural selenites with different transition metals, i.e., Li13M(SeO3)8 (M = Sc, Cr, and Fe), have been also successfully obtained in phase pure forms using similar synthetic methods. Magnetic properties, spectroscopic characterizations, and local dipole moments calculations for all the synthesized selenites are presented.

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bones, polar Li6(Mo2O5)3(SeO3)640 exhibits strong secondharmonic generation (SHG) properties, and LiSc(SeO3)2· xH2O41 shows extremely high temperature single-crystal to single-crystal transformation reactions. In this paper, we introduce a novel lithium rich manganese selenite, Li13Mn(SeO3)8, that is composed of both types of Jahn−Teller distortive cations, namely, Mn3+ and Se4+. The temperaturedependent phase transition, phase pure syntheses, and structural determination of other isostructural selenites containing different transition metals, Li13M(SeO3)8 (M = Sc, Cr, and Fe), magnetic properties, and local dipole moments calculations for the newly discovered selenites are presented.

INTRODUCTION Oxides containing Se4+ cations have been of extraordinary interest to the broad inorganic solid state chemistry field. Specifically, selenium dioxide (SeO2) exhibiting a very low triple point and an excellent aqueous solubility has been extensively used for the syntheses of new selenites as a flux in many solid state reactions as well as most solvothermal reactions with other oxide materials.1 The excellent reactivity of SeO2 with a variety of other metal cations resulted in a number of novel selenites exhibiting fascinating physicochemical characteristics such as magnetic properties2−6 and wateroxidation catalysis.7 In addition, the asymmetric coordination environment of Se4+ attributed to the stereochemically active lone pair often induced the solid state compounds to crystallize in macroscopic noncentrosymmetric (NCS) space groups, which subsequently revealed very interesting second-order nonlinear optical (NLO) properties.8−21 The overall centricity and the framework structures have been successfully controlled by the size of the constituted cations.22−28 Moreover, rich structural chemistry with variable structural dimensions has been demonstrated in many mixed metal selenites by introducing a variety of polyhedra of other metal cations during the syntheses.29−34 We have investigated a system containing lithium transition metal selenites in order to expand the selenite chemistry further. Thus far, several lithium containing selenite materials exhibiting captivating properties have been reported.24,35−41 For example, Li5Mn2(SeO3)837 and LiFe(SeO3)38 contain magnetic ions in their extended back© XXXX American Chemical Society

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EXPERIMENTAL SECTION

Li2CO3 (Hayashi, 98%), Sc2O3 (Alfa Aesar, 99.4%), Cr2O3 (Duksan, 99%), Mn2O3 (Aldrich, 99%), Fe2O3 (Kanto, 99%), SeO2 (Alfa Aesar, 99.4%), and HCl (Aldrich, 37 wt %) were used as received. Single crystals of Li13M(SeO3)8 (M = Sc, Mn, and Fe) were obtained through hydrothermal reactions. For Li13M(SeO3)8, 6.00 × 10−3 mol (0.443 g) of Li2CO3, 5.00 × 10−4 mol of M2O3, 4.00 × 10−3 mol (0.444 g) of SeO2, 2 mL of water, and 0.6 mL of HCl (aq 37 wt %) were mixed. After stirring with magnetic stirrer bars, all reaction mixtures were transferred to separate 23 mL Teflon-lined autoclaves and tightly sealed. The autoclaves were gradually heated to 230 °C [200 °C for Li13Sc(SeO3)8] and dwelled for 3 days. After heating, the reactors were cooled to room temperature at a rate of 6 °C h−1. The Received: June 19, 2017

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DOI: 10.1021/acs.inorgchem.7b01552 Inorg. Chem. XXXX, XXX, XXX−XXX

Article

Inorganic Chemistry Table 1. Crystallographic Data for Li13M(SeO3)8 (M = Mn, Sc, Cr, and Fe)

a

formula

Li13MnSe8O24

Li13MnSe8O24

Li13ScSe8O24

Li13CrSe8O24

Li13FeSe8O24

fw space group a (Å) b (Å) c (Å) α (deg) β (deg) γ (deg) V (Å3) Z T (K) λ (Å) ρcalcd (g cm−3) R(F)a or Rpb Rw(F02)c or Rwpd

1160.84 R3̅ (No. 148) 9.6037(3) 9.6037(3) 21.9175(5) 90 90 120 1750.65(12) 3 298.0(2) 0.71073 3.303 0.0209 0.0456

1160.84 P1̅ (No. 2) 9.0720(18) 9.1450(18) 9.2130(18) 62.50(3) 63.26(3) 63.50(3) 577.4(3) 1 100.0(2) 0.65000 3.339 0.0534 0.1532

1150.86 R3̅ (No. 148) 9.6240(3) 9.6240(3) 22.4298(5) 90 90 120 1799.15(14) 3 298.0(2) 0.71073 3.187 0.0398 0.0903

1157.89 R3̅ (No. 148) 9.57663(6) 9.57663(6) 21.79040(17) 90 90 120 1730.70(3) 3 298.0(2) 1.5418 3.333 0.0441 0.0587

1161.75 R3̅ (No. 148) 9.5985(2) 9.5985(2) 21.9577(3) 90 90 120 1751.96(8) 3 298.0(2) 0.71073 3.303 0.0277 0.0660

R(F) = ∑||Fo| − |Fc||/∑|Fo|. bRp = ∑|Io − Ic|/∑Io. cRw(Fo2) = [∑w(Fo2 − Fc2)2/∑w(Fo2)2]1/2. dRwp = [∑w|Io − Ic|2/∑wIo2]1/2.

products were isolated by filtration and washed with water. Hexagonal plate single crystals of Li13Sc(SeO3)8, Li13Mn(SeO3)8, and Li13Fe(SeO3)8 were isolated in 92%, 66%, and 39% yields, respectively, based on the corresponding transition metal oxides. Pure polycrystalline Li13M(SeO3)8 (M = Sc, Cr, Mn, and Fe) were synthesized by solid state reactions. For Li13Sc(SeO3)8, 2.26 × 10−3 mol (0.167 g) of Li2CO3, 1.74 × 10−4 mol (0.024 g) of Sc2O3, and 2.78 × 10−3 mol (0.308 g) of SeO 2 were combined. For Li13Cr(SeO3)8, 2.25 × 10−3 mol (0.166 g) of Li2CO3, 1.73 × 10−4 mol (0.026 g) of Cr2O3, and 2.76 × 10−3 mol (0.307 g) of SeO2 were combined. For Li13Mn(SeO3)8, 2.24 × 10−3 mol (0.166 g) of Li2CO3, 1.72 × 10−4 mol (0.027 g) of Mn2O3, and 2.76 × 10−3 mol (0.306 g) of SeO2 were combined. For Li13Fe(SeO3)8, 2.24 × 10−3 mol (0.166 g) of Li2CO3, 1.72 × 10−4 mol (0.025 g) of Fe2O3, and 2.76 × 10−3 mol (0.306 g) of SeO2 were combined. Each reaction mixture with an amount of about 0.4 g was intimately ground and pressed into pellets. The pellets were put into about 20 cm long fused silica tubes (o.d. = 0.5 cm) and evacuated. After sealing, the tubes were slowly heated to 500 °C and held at that temperature for 24 h. After cooling, the silica tubes were broken and the reaction products were washed with water to remove a small amount of unknown impurities. Phase purity for the synthesized materials was confirmed by powder X-ray diffraction (PXRD). Single crystal X-ray diffraction measurements were performed at room temperature using a Bruker SMART BREEZE diffractometer (Mo Kα radiation) containing a 1K CCD area detector. The obtained diffraction data were integrated using the program SAINT,42 and an absorption correction was applied with the program SADABS.43 For Li13Mn(SeO3)8 and Li13Fe(SeO3)8, the diffraction data were also obtained at 100 K on BL2D-SMC at the Pohang Light Source II using 0.65000 Å radiation to examine the phase transitions. All of the diffraction data were solved using SHELXS-9744 and refined with SHELXL-97.45 Powder X-ray diffraction was used to refine the crystal structure of Li13Cr(SeO3)8. The diffraction data were collected on a Bruker D8-Advance diffractometer using Cu Kα radiation at 40 kV and 40 mA. The polycrystalline sample of Li13Cr(SeO3)8 was placed tightly on a sample holder, and the data were obtained in the 2θ range of 5− 120° with a step time of 0.65 s and a step size of 0.02°. The data were refined using the Rietveld method with the program TOPAS using the single crystal data of Li13Mn(SeO3)8 as a starting model. The March− Dollase function was applied to correct a preferred orientation along the [003] direction during the refinement. Thermal properties for the title compounds were studied using a SCINCO TGA-N 1000 thermal analyzer. The ground samples were loaded in alumina crucibles and heated to 900 °C under flowing argon at a rate of 10 °C min−1. UV−vis diffuse reflectance spectra were obtained using a Varian Cary 500 scan UV−vis−NIR spectrophotometer at room temperature.

The collected reflectance spectra were converted to the absorbance data using the Kubelka−Munk function.46,47 IR spectra were acquired by a Thermo Scientific Nicolet iS10 FT-IR spectrometer using samples intimately touched by a diamond attenuated total reflectance (ATR) crystal. Energy dispersive analyses by X-ray (EDX) attached to a scanning electron microscope (SEM) were performed by a Hitachi S-3400N and a Horiba Energy EX-250. EDX for Li13M(SeO3)8 (M = Sc, Cr, Mn, and Fe) exhibit approximate M:Se ratios of 1:8. The dc magnetic susceptibilities for polycrystalline Li13M(SeO3)8 (M = Cr, Mn, and Fe) were measured using a Quantum Design Magnetic Properties Measurement System (MPMS-XL7) for zero-field cooled (ZFC) and field cooled (FC) modes. The static susceptibilities were collected in the temperature range 2−300 K with an applied field of 100−1000 Oe. Isothermal magnetization curves were measured in a field range of −7 to 7 T at 2 K.

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RESULTS AND DISCUSSION Hexagonal-shaped single crystals of Li13Mn(SeO3)8 were obtained through a hydrothermal reaction by using Li2CO3, Mn2O3, SeO2, and water at 230 °C for 3 days (66% yield based on Mn2O3). Pure polycrystalline Li13Mn(SeO3)8 was also synthesized by a solid state reaction using the intimately mixed same reactants that were heated in a sealed fused silica tube at 500 °C for 24 h. Single crystal X-ray diffraction measurements performed at room temperature indicated that Li13Mn(SeO3)8 crystallizes in the symmetric trigonal space group, R3̅ (No. 148) (see Table 1). Li13Mn(SeO3)8 reveals a molecular structure that is composed of MnO6 octahedra, SeO3 trigonal pyramids, and Li+ cations (see Figure 1). The unique Mn3+ cation is coordinated by six oxide ligands in an octahedral environment with six identical Mn−O bond lengths of 2.016(2) Å. Two kinds of Se4+ cations that are linked by three oxygen atoms in trigonal pyramidal moieties exist within an asymmetric unit with the Se−O bond distances ranging from 1.670(2) to 1.735(2) Å. Among three unique Li+ cations in an asymmetric unit, Li(1)+ interacts with six oxygen atoms in octahedral environments, whereas Li(2)+ and Li(3)+ are contacted by four oxygen atoms in tetrahedral moieties with the Li−O contact distances of 1.945(6)−2.165(2) Å. The MnO6 octahedron is linked by six Se(1)O3 polyhedra through O(1), which results in a huge molecular structure of Li13Mn(SeO3)8 (see Figure 1). As seen in Figure 1, the Se(2)O3 trigonal pyramid further interacts with Li(2)+ and Li(3)+ cations through O(4). The connectivity B

DOI: 10.1021/acs.inorgchem.7b01552 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry

Mn−O bond distances are observed at 100 K through the Jahn−Teller distortion (see Figure 3). In triclinic Li13Mn(SeO3)8, four unique Se4+ cations are in trigonal pyramidal geometries with Se−O bond lengths ranging from 1.674(4) to 1.748(4) Å. Also, seven unique Li+ cations exist in an asymmetric unit, having contacts with four and six oxygen atoms with Li−O contact lengths of 1.861(12)−2.203(4) Å. In order to establish the dynamic Jahn−Teller effect further, a series of isostructural lithium-rich transition metal selenites, Li13M(SeO3)8 (M = Sc, Cr, and Fe), were also synthesized in phase pure forms. Detailed synthesis condition and structural characterization can be found in the Supporting Information. As expected, Li13Sc(SeO3)8, Li13Cr(SeO3)8, and Li13Fe(SeO3)8 containing high spin d0, d3, and d5 ions, respectively, revealed six equivalent M−O bond lengths in ideal MO6 octahedral environment at room temperature. In order to confirm the phenomena, synchrotron X-ray diffraction measurements at 100 K for one of the selenites, Li13Fe(SeO3)8, were also carried out. Although a small decrease in volume was found at 100 K, however, no phase transition occurred from Li13Fe(SeO3)8 with a high spin d5 configuration. The synthesized materials also possess a family of secondorder Jahn−Teller (SOJT) distortive cation, Se4+. Because the Se4+ cation contains a stereoactive lone pair, the extent of asymmetric environment can be understood by calculating the local dipole moments.52−54 The determined dipole moments for the asymmetric SeO3 polyhedra range from 7.9 to 9.6 debye (D), which are consistent with those for previously reported selenites (see Table 2).18,22−27,29−32,34,41 Thermal analyses indicate that Li13Sc(SeO3)8, Li13Cr(SeO3)8, Li13Mn(SeO3)8, and Li13Fe(SeO3)8 are thermally stable up to 620, 570, 500, and 540 °C, respectively. Above the temperatures, each material decomposes perhaps attributed to the volatilization of SeO2 at higher temperatures. Powder X-ray diffraction patterns measured after heating the materials to 600 and 700 °C reveal unknown mixtures of materials. The TGA diagrams for the lithium metal selenites have been deposited to the Supporting Information. Using the UV−vis diffuse reflectance spectral data, band gaps for the reported materials have been calculated with the Kubelka−Munk function.46,47 Specifically, the gaps were obtained in the K/S versus E plots by extrapolating the linear part of the increasing curves to zero (K, absorption; S, scattering; E, energy; see Figure 4a). By doing so, the band gaps for Li13Sc(SeO3)8, Li13Cr(SeO3)8, Li13Mn(SeO3)8, and Li13Fe(SeO3)8 were calculated to be approximately 3.3, 3.2, 2.8, and 4.7 eV, respectively. The main difference in gaps for the title compounds may be attributable to the extent of 3d orbitals involved in the conduction bands in the backbones as well as the distortions occurring from SeO3 polyhedra. Also, the peaks found in IR spectra for all four reported materials confirmed the existence of M−O and Se−O bonds (see Figure 4b). While the bands occurring at around 400−570 cm−1 are due to M−O vibrations, those found at about 650−850 cm−1 are attributable to Se−O bonds.55 The magnetic susceptibility of Li13M(SeO3)8 (M = Cr, Mn, and Fe) is shown in Figure 5. There is no splitting between ZFC and FC curves over all temperatures. We find no indication to long-range magnetic ordering down to T = 2 K. The magnetic susceptibility of Li13M(SeO3)8 is fitted with the Curie−Weiss law, χ(T) = C/(T − ΘCW) + χ0, where C is the Curie constant, ΘCW is the Weiss temperature, and χ0 represents the temperature-independent part of the magnetic

Figure 1. ORTEP (50% probability ellipsoids) drawing of Li13Mn(SeO3)8 revealing a molecular structure composed of MnO6 octahedra, SeO3 trigonal pyramids, and Li+ cations.

of Li13Mn(SeO3)8 may be described as anionic molecules of {[MnO6/2]3− 6[SeO1/2O2/1]1− 2[SeO3/1]2−}13− with the charge neutrality retained by the Li+ cations. The structural description of Li13Mn(SeO3)8 can be approached differently by considering the Li−O interactions. Li(1)O 6 , Li(2)O 4 , and Li(3)O 4 polyhedra share their oxide ligands and form layers in the abplane (see Figure 2a). The Se(1)O3 and Se(2)O3 groups further cap the layers from above and below along the approximate c-direction (see Figure 2b). Then the MnO6 octahedra serve as interlayer linkers by connecting each layer through O(2) and O(3) (see Figure 2c). Thus, the framework of Li13Mn(SeO3)8 may be described as a pseudo-threedimensional structure. Within the framework, 8-membered ring (8-MR) channels composed of MnO6 and SeO3 groups are running along the [010] direction as seen in Figure 2c. The lone pairs on Se4+ cations point to the center of 8-MR channels. Bond valence sum calculations48 for the Li+, Mn3+, and Se4+ reveal values of 0.90−1.05, 2.98, and 4.04−4.09, respectively. It should be noticed that all six Mn−O bond distances for MnO6 octahedra in Li13Mn(SeO3)8 are identical. In other words, a strong Jahn−Teller effect expected for the compound containing Mn3+ cation with high spin d4 configuration has not been observed, which should be attributable to the dynamic Jahn−Teller effect at room temperature.49−51 Synchrotron Xray diffraction data obtained at 100 K using 0.65000 Å radiation, however, indicate that Li13Mn(SeO3)8 transforms from the trigonal space group, R3̅ to the triclinic space group, P1̅ (see Table 1). Although similar structural backbones are observed, the two axial Mn−O bonds in MnO6 octahedra elongate at 100 K. While six Mn−O bond lengths were equivalent [2.016(2) Å] at room temperature, four intermediate [1.946(4)−1.953(4) Å] and two long [2.166(4) Å] C

DOI: 10.1021/acs.inorgchem.7b01552 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry

Figure 2. (a) A layered structure is obtained by the combination of LiO6 and LiO4 polyhedra in the ab-plane. (b) The SeO3 groups cap the layer from above and below along the approximate c-direction. (c) The interlayer linking of MnO6 octahedra results in a pseudo-three-dimensional structure of Li13Mn(SeO3)8. Note that the lone pairs on Se4+ cations point to the center of 8-MR channels (blue, Mn; green, Se; red, O; yellow, Li).

Table 2. Calculation of Local Dipole Moments for SeO3 Polyhedra in Li13M(SeO3)8 (M = Sc, Cr, Mn, and Fe) compound

species

dipole moment (Da)

Li13Sc(SeO3)8

Se(1)O3 Se(2)O3 Se(1)O3 Se(2)O3 Se(1)O3 Se(2)O3 Se(1)O3 Se(2)O3

9.6 8.7 9.6 7.9 9.4 8.3 9.4 8.4

Li13Cr(SeO3)8 Li13Mn(SeO3)8 Li13Fe(SeO3)8 a

Debye.

susceptibility (see the solid lines in Figure 5). The fitting parameters of the Curie−Weiss law are tabulated in Table 3. The effective magnetic moments are estimated to μeff = 3.59 μB/Cr3+, 4.68 μB/Mn3+, and 5.48 μB/Fe3+. The obtained values are close to the spin-only vales of μeff = 3.87 μB/Cr3+, 4.89 μB/ Mn3+, and 5.91 μB/ Fe3+, implying the quenching of orbital momentum. ΘCW has a very small value for all M ions, indicative of a negligible exchange interaction. In fact, the M3+ ions are coupled via longer-range exchange path M−O−Se− O−Se−O−M along the c-axis. Here we note that the magnetic susceptibility of Li13Mn(SeO3)8 shows a substantial deviation from the Curie−Weiss behavior for temperatures below 35 K, which may be ascribed to a small amount of γ-Mn2O3 undergoing a ferromagnetic transition below 39 K.

Figure 3. Li13Mn(SeO3)8 containing high spin d4 configuration reveals six identical Mn−O bond distances at room temperature attributable to the dynamic Jahn−Teller effect. At 100 K, however, an elongation through the Jahn−Teller effects results in four intermediate and two long Mn−O bonds in Li13Mn(SeO3)8.

D

DOI: 10.1021/acs.inorgchem.7b01552 Inorg. Chem. XXXX, XXX, XXX−XXX

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Figure 4. (a) UV−vis diffuse reflectance and (b) IR spectra for Li13M(SeO3)8 (M = Sc, Cr, Mn, and Fe).

The isothermal magnetization M(H) of Li13M(SeO3)8 was measured at T = 2 K in a field range from −7 to 7 T. M(H) values of Li13Cr(SeO3)8 and Li13Fe(SeO3)8 are well described by the Brillouin function, confirming that the exchange interactions of Cr3+ and Fe3+ ions are not bigger than 2 K. In contrast, the magnetization curve of Li13Mn(SeO3)8 exhibits a steep increase in the field up to 0.2 T and then a linear increase with increasing field. The magnetization is expected to saturate around 10 T at Ms = 5 μB. The linear component arises from the presence of sizable antiferromagnetic interactions of Mn3+ ions while the low-field increase is due to the γ-Mn2O3 impurity. The magnetization curve is well fitted by a sum of the Brillouin function and χH. Compared to Cr3+ or Fe3+ ions, the magnetic interaction of Mn3+ is enhanced possibly due to the dynamic Jahn−Teller distortion of MnO6.

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CONCLUSIONS A series of new lithium rich transition metal selenites, Li13Sc(SeO3)8, Li13Cr(SeO3)8, Li13Mn(SeO3)8, and Li13Fe(SeO3)8, have been synthesized through hydrothermal and solid state reactions. The isostructural selenites, Li13M(SeO3)8, reveal pseudo-three-dimensional structures that are composed of LiO4, LiO6, SeO3, and MO6 groups. While the MnO6 octahedra in Li13Mn(SeO3)8 containing high spin d4 configuration exhibit six equivalent Mn−O bond lengths at room

Figure 5. Dc magnetic susceptibility of (a) Li13Cr(SeO3)8, (b) Li13Mn(SeO3)8, and (c) Li13Fe(SeO3)8 as a function of temperature. The black solid lines represent Curie−Weiss fits. The isothermal magnetization curves of (d) Li13Cr(SeO3)8, (e) Li13Mn(SeO3)8, and (f) Li13Fe(SeO3)8 measured at T = 2 K. The black solid lines represent Brillouin function fits.

temperature owing to the dynamic Jahn−Teller effect, an elongation of the MnO6 octahedra is observed at 100 K. The E

DOI: 10.1021/acs.inorgchem.7b01552 Inorg. Chem. XXXX, XXX, XXX−XXX

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(5) Zimmermann, I.; Johnsson, M. Synthesis and Crystal Structure of the Solid Solution Co3(SeO3)3‑x(PO3OH)x(H2O) Involving Crystallographic Split Positions of Se4+ and P5+. Inorg. Chem. 2013, 52, 11792− 11797. (6) Hu, S.; Johnsson, M.; Law, J. M.; Bettis, J. L., Jr.; Whangbo, M.H.; Kremer, R. K. Crystal Structure and Magnetic Properties of FeSeO3F - Alternating Antiferromagnetic S = 5/2 chains. Inorg. Chem. 2014, 53, 4250−4256. (7) Rabbani, F.; Svengren, H.; Zimmermann, I.; Hu, S.; Laine, T.; Hao, W.; Åkermark, B.; Åkermark, T.; Johnsson, M. Cobalt selenium oxohalides: catalysts for water oxidation. Dalton Trans. 2014, 43, 3984−3989. (8) Kim, S.-H.; Yeon, J.; Halasyamani, P. S. Noncentrosymmetric Polar Oxide Material, Pb3SeO5: Synthesis, Characterization, Electronic Structure Calculations, and Structure-Property Relationships. Chem. Mater. 2009, 21, 5335−5342. (9) Chang, H. Y.; Kim, S. W.; Halasyamani, P. S. Polar Hexagonal Tungsten Oxide (HTO) Materials: (1) Synthesis, Characterization, Functional Properties, and Structure-Property Relationships in A2(MoO3)3(SeO3) (A = Rb+ and Tl+) and (2) Classification, Structural Distortions, and Second-Harmonic Generating Properties of Known Polar HTOs. Chem. Mater. 2010, 22, 3241−3250. (10) Lee, D. W.; Oh, S.-J.; Halasyamani, P. S.; Ok, K. M. New Quaternary Tellurite and Selenite: Synthesis, Structure, and Characterization of Centrosymmetric InVTe2O8 and Noncentrosymmetric InVSe2O8. Inorg. Chem. 2011, 50, 4473−4480. (11) Nguyen, S. D.; Kim, S.-H.; Halasyamani, P. S. Synthesis, Characterization, and Structure-Property Relationships in Two New Polar Oxides: Zn2(MoO4)(SeO3) and Zn2(MoO4)(TeO3). Inorg. Chem. 2011, 50, 5215−5222. (12) Kong, F.; Hu, C.-L.; Xu, X.; Zhou, T.-H.; Mao, J.-G. Syntheses, crystal structures and SHG properties of a series of polar alkali-metal m o l y b d e n u m ( V I ) s e l e n i t e s b a s e d o n S tr a n d b e r g - t y p e [Mo5O15(SeO3)2]4‑ polyanion. Dalton Trans. 2012, 41, 5687−5695. (13) Olshansky, J. H.; Thao Tran, T.; Hernandez, K. J.; Zeller, M.; Halasyamani, P. S.; Schrier, J.; Norquist, A. J. Role of HydrogenBonding in the Formation of Polar Achiral and Nonpolar Chiral Vanadium Selenite Frameworks. Inorg. Chem. 2012, 51, 11040−11048. (14) Yeon, J.; Kim, S.-H.; Nguyen, S. D.; Lee, H.; Halasyamani, P. S. New Vanadium Selenites: Centrosymmetric Ca2(VO2)2(SeO3)3(H2O)2, Sr2(VO2)2(SeO3)3, and Ba(V2O5)(SeO3), and Noncentrosymmetric and Polar A4(VO2)2(SeO3)4(Se2O5) (A = Sr2+ or Pb2+). Inorg. Chem. 2012, 51, 609−619. (15) Cao, X.-L.; Hu, C.-L.; Xu, X.; Kong, F.; Mao, J.-G. Pb2TiOF(SeO3)2Cl and Pb2NbO2(SeO3)2Cl: small changes in structure induced a very large SHG enhancement. Chem. Commun. 2013, 49, 9965−9967. (16) Lee, E. P.; Song, S. Y.; Lee, D. W.; Ok, K. M. New Bismuth Selenium Oxides: Syntheses, Structures, and Characterizations of Centrosymmetric Bi2(SeO3)2(SeO4) and Bi2(TeO3)2(SeO4) and Noncentrosymmetric Bi(SeO3)(HSeO3). Inorg. Chem. 2013, 52, 4097−4103. (17) Nguyen, S. D.; Halasyamani, P. S. Synthesis, Structure, and Characterization of Two New Polar Sodium Tungsten Selenites: Na2(WO3)3(SeO3)·2H2O and Na6(W6O19)(SeO3)2. Inorg. Chem. 2013, 52, 2637−2647. (18) Kim, Y. H.; Lee, D. W.; Ok, K. M. Noncentrosymmetric YVSe2O8 and Centrosymmetric YVTe2O8: Macroscopic Centricities Influenced by the Size of Lone Pair Cation Linkers. Inorg. Chem. 2014, 53, 1250−1256. (19) Cao, X.-L.; Hu, C.-L.; Kong, F.; Mao, J.-G. Explorations of New SHG Materials in the Alkali-Metal-Nb5+-Selenite System. Inorg. Chem. 2015, 54, 10978−10984. (20) Cao, X.-L.; Hu, C.-L.; Kong, F.; Mao, J.-G. Cs(TaO2)3(SeO3)2 and Cs(TiOF)3(SeO3)2: Structural and Second Harmonic Generation Changes Induced by the Different d0-TM Coordination Octahedra. Inorg. Chem. 2015, 54, 3875−3882.

Table 3. Results of Curie−Weiss Fits for Li13M(SeO3)8 (M = Cr, Mn, and Fe) compound

C (emu K mol−1)

μeff (μB)

ΘCW (K)

χ0 (emu mol−1 Oe−1)

Li13Cr(SeO3)8 Li13Mn(SeO3)8 Li13Fe(SeO3)8

1.62(1) 2.7(1) 3.7(1)

3.59 4.68 5.48

−1.4(5) −5.8(2) −1.2(3)

0.0016(6) 0.0014(5) 0.0027(4)

band gaps for Li13Sc(SeO3)8, Li13Cr(SeO3)8, Li13Mn(SeO3)8, and Li13Fe(SeO3)8 are calculated to be about 3.3, 3.2, 2.8, and 4.7 eV, respectively. Magnetic properties measurements indicate that Li13M(SeO3)8 (M = Cr, Mn, and Fe) are paramagnetic down to 2 K.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.7b01552. Experimental details, calculated and observed X-ray diffraction patterns, thermogravimetric analysis diagrams, and EDX data (PDF) Accession Codes

CCDC 1556762−1556765 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.

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AUTHOR INFORMATION

Corresponding Author

*Tel: +82-2-820-5197. Fax: +82-2-825-4736. E-mail: kmok@ cau.ac.kr. ORCID

Kang Min Ok: 0000-0002-7195-9089 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This research was supported by the National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT and Future Planning (Grant 2016R1A2A2A05005298). We acknowledge Prof. Y. Lee (KAIST) in obtaining the synchrotron X-ray diffraction data.

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REFERENCES

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DOI: 10.1021/acs.inorgchem.7b01552 Inorg. Chem. XXXX, XXX, XXX−XXX