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

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Deep-Ultraviolet Mixed-Alkali-Metal Borates with Induced Enlarged Birefringence Derived from the Structure Rearrangement of the LiB3O5 Qian Wang,† Fei Yang,† Xing Wang,† Jing Zhou,† Jia Ju,‡ Ling Huang,*,† Daojiang Gao,† Jian Bi,† and Guohong Zou*,§ †

College of Chemistry and Materials Science, Sichuan Normal University, Chengdu 610068, People’s Republic of China Institute of Chemical Materials, China Academy of Engineering Physics, Mianyang 621900, People’s Republic of China § College of Chemistry, Sichuan University, Chengdu 610064, People’s Republic of China

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‡

S Supporting Information *

ABSTRACT: By introduction of K+, Rb+, and Cs+ cations into the classical commercial nonlinear optical crystal LiB3O5 (LBO), the series of novel mixed-alkali-metal borates Li 2 . 6 K 0 . 4 [B 5 O 8 (OH) 2 ] (K-LBO), Li2.85Rb0.15[B5O8(OH)2] (Rb-LBO), and Li2.9Cs0.1[B5O8(OH)2] (Cs-LBO) have been obtained under hydrothermal conditions. The steric hindrance effect generated by the introduction of large alkali-metal cations and partial substitution of small Li+ cations broke the three-dimensional (3-D) framework of [B3O7]5− borate−oxygen clusters in LBO and resulted in a structure rearrangement to produce infrequent [B10O26]22− 2-D layers. The unique layered structure induced an increase in birefringence in A-LBOs (A = K, Rb, Cs), which is favorable for phase matching during second-harmonic generation. All three compounds are potential deep-ultraviolet nonlinear optical materials, which was proved by UV−vis−NIR diffuse reflectance spectroscopy and second-harmonic-generation measurements.

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LiB3O5 (LBO),18 despite their wide transmittance spectrum and large second-harmonic-generation (SHG) effect, their inappropriate birefringence limits their practical application in the DUV region. Recent experimental and theoretical calculation investigations proved that the synthesis of new DUV NLO materials with large SHG coefficient or short cutoff edges can be easily realized through molecular crystal engineering. A series of potential NLO crystals, for instance, BPO4,19 K3B6O10Cl,20 NaSr3Be3B3O9F4,21 Ba4B11O20F,22 Ba3(ZnB5O10)PO4,23 etc., have been developed. Though their absorption edges are very short, far below 200 nm, their SHG limit cannot reach the DUV region due to the infeasibility of phase matching caused by their small birefringence. On the basis of the above facts, crystallographers have proposed the “birefringence challenge”.24 It is at the forefront of research and remains an ongoing challenge in the design and synthesis of novel NLO materials with moderate birefringence, especially in the UV and deep-UV regions. On the basis of the summary and analysis of existing optical materials, a layered structure is favorable for generating moderate birefringence.25−27 At present, though other chemical systems28−30 have been developed to explore new DUV NLO materials, borates31,32 are still the most promising

INTRODUCTION Deep-ultraviolet (DUV) nonlinear optical (NLO) crystals have attracted intense attention in the laser and photonic fields, such as high-resolution spectroscopy, nanomicro machining, laser cooling, material processing, and photolithography, as DUV coherent light (λ < 200 nm) can be produced through direct frequency doubling.1−10 In earlier research, DUV NLO materials mainly focused on borates. Recently though, researchers have developed several alternative chemical systems such as phosphates,11 carbonates,12,13 nitrates, etc.14,15 for the exploration of novel DUV NLO crystals through continuous efforts; KBe2BO3F2 (KBBF)16 remains the only NLO material that is available to obtain DUV coherent light through sixth-harmonic generation up to now. Its practical application is severely restricted due to two fatal weaknesses: the hypertoxicity of the raw materials and the strong layered habits in crystal growth. Hence, the exploration of novel DUV NLO materials remains a huge challenge and is in urgent demand. Generally speaking, an acceptable DUV NLO material should possess comprehensive performance including deep UV transparency, relatively strong SHG coefficient (∼0.39 pm/V), and appropriate birefringence (0.05−0.1). It is difficult to realize “three in one”, one compound simultaneously exhibiting the three aforementioned properties. For example, the famous commercial crystals β-BaB2O4 (β-BBO)17 and © XXXX American Chemical Society

Received: January 28, 2019

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DOI: 10.1021/acs.inorgchem.9b00271 Inorg. Chem. XXXX, XXX, XXX−XXX

Article

Inorganic Chemistry

Table 1. Crystal Data and Structure Refinement Details for Li2.6K0.4[B5O8(OH)2] (K-LBO), Li2.85Rb0.15[B5O8(OH)2] (RbLBO), and Li2.9Cs0.1[B5O8(OH)2] (Cs-LBO) formula mass (amu) cryst syst space group a (Å) b (Å) c (Å) α (deg) γ (deg) V (Å3) Z ρ(calcd) (g/cm3) temp (K) λ (Å) F(000) μ (mm−1) R1/wR2 (I> 2σ(I))a R1/wR2 (all data) GOF on F2

Li2.6K0.4[B5O8(OH)2]

Li2.85Rb0.15[B5O8(OH)2]

Li2.9Cs0.1[B5O8(OH)2]

249.75 orthorhombic Pnc2 8.2856(14) 8.8138(15) 9.3644(16) 90 90 683.9(2) 1 2.432 150(2) 0.71073 491 0.472 0.0420/0.0940 0.0572/0.1018 1.044



R1(F) = ∑||Fo| − |Fc||/∑|Fo|. wR2(Fo2) = [∑w(Fo2 − Fc2)2/∑w(Fo2)2]1/2.

a

A-LBOs (A = K, Rb, Cs) were synthesized via a hydrothermal method. The reaction materials contain LiB3O5, ACl (A = K, Rb, Cs), and 5 mL of deionized water. The loaded components are as follows: LiB3O5 (0.339 g, 2.85 mmol) and KCl (0.075g, 1 mmol) for Li2.6K0.4[B5O8(OH)2] (K-LBO), LiB3O5 (0.339 g, 2.85 mmol) and RbCl (0.084 g, 0.5 mmol) for Li2.85Rb0.15[B5O8(OH)2] (Rb-LBO), and LiB3O5 (0.339 g, 2.85 mmol) and CsCl (0.084 g, 0.5 mmol) for Li2.9Cs0.1[B5O8(OH)2] (Cs-LBO). All of the mixtures were stirred at room temperature for 20 min, and the initial pH values were about 9.0. Then the reactants were sealed into a 23 mL autoclave with a Teflon liner, heated at 220 °C for 5 days, and then slowly cooled to ambient temperature at a rate of 5 °C/h. Transparent rodlike crystals of A-LBOs (A = K, Rb, Cs) were obtained, washed with deionized water, and dried in air. The yields of the three compounds were 11%, 6%, 5% (based on K, Rb, and Cs), respectively. Extremely pure crystals are difficult to synthesize because of impurities and the tiny size of crystals. Hence, only K-LBO of the three isostructural compounds has been thoroughly synthesized for property characterizations. Single-Crystal Structure Determination. Single-crystal data of K-LBO, Rb-LBO, and Cs-LBO were collected at 150 K on a Bruker D8 Venture diffractometer using graphite-monochromated Mo Kα radiation. A multiscan technique was used to do the absorption correction. The structures were solved by direct methods and refined by full-matrix least-squares fitting on F2 using SHELX-2014.43,44 All non-hydrogen atoms were refined anisotropically; it is difficult to determine the exact sites of the hydrogen atoms in the three compounds, and all of the hydrogen atoms were set in geometrically calculated positions or in a difference Fourier map. K+, Rb+, Cs+, and a part of the Li+ ions in the three compounds are crystallographically disordered; a similar situation can also be found in other crystals.45−47 The three structures were also checked with PLATON, and no possible missing symmetries could be found.48 Crystallographic data and structural refinements for K-LBO, Rb-LBO, and Cs-LBO are summarized in Table 1. The remaining related crystallographic data are summarized in Tables S1−S6. Powder X-ray Diffraction. The powder X-ray diffraction data of K-LBO were recorded using a Rigaku MiniFlex 600 powder X-ray diffractometer with Cu Kα radiation (λ = 1.540598 Å) at room temperature. The angular 2θ values are in the range of 5−70°with a step size of 0.02° and a fixed time of 0.2 s per step. Thermal Analysis. Thermogravimetric analysis of K-LBO was performed on a Discovery thermal analyzer instrument, and the

candidates due to excellent optical performance and structural diversity. It has been demonstrated that designing new functional materials by adjusting the arrangement of boron− oxygen functional building blocks in classical borates using a substitution strategy is an effective method. For instance, AZn2BO3X2 (A = K, Rb, NH4; X = Cl, Br),33 Cs3Zn6B9O21,34 and Rb3Al3B3O10F35 derived from KBBF successfully solve the toxicity of beryllium and layered habit in crystal growth. In addition, MM′Be2B2O6F (M = Na, K; M′ = Ca, Sr)36 and K3 M 3 Li2 Al4B 6O 20 F (M = Sr, Ba)37,38 stemming from Sr2Be2B2O7 (SBBO)39 overcome the structural instability. Especially, through partial replacement of the O atoms with F atoms in the BO4 units, Pan’s group developed fluorooxoborates,40−42 a new branch of borates, exhibiting improved birefringence in the DUV region which have been considered to be ideal next-generation DUV NLO materials. Also, the introduction of alkali-metal cations with different sizes could regulate the boron−oxygen cluster network to exhibit different dimensions. Guided by above ideas, we have successfully synthesized the three new mixed-alkali-metal borates Li2.6K0.4[B5O8(OH)2] (K-LBO), Li2.85Rb0.15[B5O8(OH)2] (Rb-LBO), and Li2.9Cs0.1[B5O8(OH)2] (Cs-LBO) by introducing large alkali-metal cations into the classical NLO crystal LiB3O5 (LBO) which exhibit a very short UV absorption edge of about 155 nm while having poor birefringence. The steric hindrance effect generated by the introduction of large alkalimetal cations and partial substitution of small Li+ cations disrupts the 3-D network of [B3O7]5− boron−oxygen clusters in LBO and makes the crystal structure rearrange to form infrequent 2-D [B10O26]22− layers in the new compounds. In addition, the formation of a unique layered structure improved the poor birefringence to push the SHG limit deeper toward the DUV region.

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EXPERIMENTAL SECTION

Synthesis of A-LBOs (A = K, Rb, Cs). KCl (Macklin, 99.5%), RbCl (Macklin, 99.5%), CsCl (Aladdin, ≥99.5%), H3BO3 (Aladdin, 99%), and Li2CO3 (Aladdin, ≥99.0%) were obtained from commercial sources. LiB3O5 was synthesized according to ref 18. B


Article

Inorganic Chemistry heating rate is set to be 10 °C/min. 10−15 mg crystal samples were placed in a platinum crucible and heated from room temperature to 800 °C under a constant flow of nitrogen atmosphere. Infrared Spectroscopy. The IR spectrum for K-LBO was collected in the range of 4000−400 cm−1, and the instrument used was a Vertex 70 Fourier transform infrared (FT-IR) spectrometer. The samples were pressed with a KBr matrix. Energy-Dispersive X-ray Spectroscopy (EDS) Analysis. Scanning electron microscopes (SEM, Quanta250; FEI and FESEM, SU-8010) were used to determine the approximate ratio of elements. The elements were qualitatively analyzed, and the results of the elemental analyses are shown in Figures S2−S4. From the analysis results, we can see the presence of the K/Rb/Cs element in the three compounds, which are in accordance with the single-crystal structure analysis. UV−Vis Diffuse Reflectance Spectroscopy. UV−vis diffuse reflectance spectroscopy of K-LBO was recorded with a PerkinElmer Lamda-950 UV/vis/NIR spectrophotometer at room temperature. Data were collected over the spectral range of 190−2500 nm. Second-Harmonic Generation. The power frequency-doubling signal of K-LBO was measured by the Kurtz and Perry method at room temperature with a 1064 nm Q-switch Nd:YAG laser on powdered samples.49 All of the samples were ground and divided into the following six distinct particle sizes: 25−45, 45−58, 58−75, 75− 106, 106−150, and 150−212 μm, respectively. Sieved powders of KDP (KH2PO4) were used as references. Computational Descriptions. Density functional theory (DFT) was used to calculate the electronic structure of K-LBO with the CASTEP module.50 The ion cores were represented with the normconserving pseudopotentials. The valence electrons H 1s1, Li 1s22s1, O 2s22p4, B 2s22p1, and K 3s23p64s1 were selected in the calculation. A 3 × 3 × 4 k-points sampling and a 650 eV plane-wave cutoff energy were used. The self-consistent convergence of the total energy was set as 1.0 × 10−6 eV/atom. All subsequent calculations were performed on this optimized geometry.51

form planar [B(4)O3] and [B(1)O3] triangles with the B−O bond lengths ranging from 1.360 to 1.380 Å, while the B(2), B(3), B(5), and B(6) atoms are bridged with four oxygen atoms and form [B(2)O4], [B(3)O4], [B(5)O4], and [B(6)O4] tetrahedra, with B−O bond lengths ranging from 1.431 to 1.529 Å. In this compound, two B(4)O3 triangles and two B(2)O4 tetrahedra are connected with one B(3)O4 tetrahedron through sharing the vertex atoms and forming a [B5O10(OH)2]7− fundamental building block (FBB), and meanwhile two B(5) atoms, two B(1) atoms, and one B(6) atom are also linked to the other similar cluster. According to the scheme proposed by Christ and Clark, the B5 pentaborate anions constructed with two BO3 triangles and three BO4 tetrahedra can be classified as 5:[2Δ + 3T] (Figure 1e).52 Further, four anions but two types of [B5O10(OH)2]7− are bridged by sharing the O8 and O3 atoms to form a rarely reported [B10O26]22− building block, and two independent B5 anions are twisting at a slight angle in comparison with the other anions, resulting in [B10O26]22− anions with two orientations (Figure 1d). Then [B10O26]22− units expand to the 2-D layers via corner sharing of oxygen atoms and are further bridged by Li+ ions to form 3-D framework with Li+ ions also arranged in two directions. Disordered K+ and Li+ ions are located in the channels along the a axis (Figure 1c). The three new compounds K-LBO, Rb-LBO, and Cs-LBO have been obtained by introducing the series of large alkali cations K+, Rb+, and Cs+ into the known UV NLO borate LBO, and all three compounds crystallize in the NCS space group Pnc2, while LBO crystallizes in the space group Pna21. The introduction of large alkali-metal cations brought about a rearrangement of LBO. As shown in Figure 2a, LBO can be

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RESULTS AND DISCUSSION Crystal Structure Description. Crystallographic measurement shows that K-LBO crystallizes in the noncentrosymmetric (NCS) space group Pnc2 (crystal system: orthorhombic). As shown in Figure 1a,b, the K atom is coordinated with eight oxygen atoms, forming a [KO8] polyhedron with K−O bond lengths from 2.395 to 2.624 Å. For B atoms, the B(4) and B(1) atoms are connected with three oxygen atoms to

Figure 2. (a) Ball and stick and polyhedron representations of the 3D B−O framework of LBO along the b axis. (b) 3-D framework of LBO along the c axis. (c) [B3O7]5− zigzag chain and helix column in LBO. (d) The “layer” arrangement in K-LBO; .(e) The B−O layer in K-LBO along the c axis. (f) [B10O26]22− units in K-LBO. Color scheme: purple tetrahedron, [BO4]5− anion; green triangle, [BO3]3− anion.

viewed as the constitution of [B3O7]5− zigzag chains, which are composed of two BO3 triangles and one BO4 tetrahedron, with the [B3O7]5− units arranged parallel with two orientations. Then four chains connect to the 10-MR-containing helix column, and all the adjacent columns are nearly vertically arranged. In LBO, borate atoms and oxygen atoms connect directly to the 3-D framework and Li+ cations are filling in the 10-MR channels and play the role of charge balance. However in K-LBO, 10-MR groups with dimensions of 6.7713(6) × 4.1016(3) Å2 are constructed of four BO3 triangles and six BO4

Figure 1. (a) Ball and stick representation of the unit cell of K-LBO. (b) Coordination environment of the K1+ cation. (c) View of the 3-D framework along the a axis. (d) The B−O 2-D layer along the c axis. (e) Ball and stick representation of two independent B5 clusters. C


Article

Inorganic Chemistry

asymmetric and symmetric vibrations of the BO4 groups are located at 1024−1056 and 907 cm−1, respectively, and the absorption bands observed at 836, 715, 680, and 631 cm−1 may be attributed to BO3/BO4 bending vibrations. The above assignments show good agreement with other reported metal borates.53,54 As shown in Figure 5, the UV−vis diffuse reflectance spectrum was collected for K-LBO. The reflectance is high

tetrahedra (Figure 2f), and boron−oxygen basic building blocks of the same type in a 10-MR group are almost oppositely arranged, which is not beneficial for the superposition of an NLO coefficient. In comparison with LBO, borate atoms and oxygen atoms only link to the 2-D layer and Li+ plays the role of connecting the layers to the 3-D framework in K-LBO (Figure 2d,e). The introduction of large alkali-metal atoms successfully breaks the 3-D framework of borate−oxygen clusters of LBO and results in a “layer”containing structure of K-LBO, which is favorable for generating a relatively large birefringence. Powder X-ray Diffraction. The powder XRD pattern of K-LBO was measured. As shown in Figure 3, the experimental pattern is in good agreement with the calculated pattern based on single-crystal X-ray diffraction results.

Figure 5. UV absorption spectrum and optical diffuse reflectance spectrum for K-LBO.

(above 75%) at a wavelength of 190 nm, which means that the UV cutoff edge of K-LBO may be below 190 nm, indicating that the title compound is a potential deep-ultraviolet optical material. NLO Properties. K-LBO is noncentrosymmetric, and the SHG response based on a 1064 nm Q-switch laser was measured. KDP was used as the reference, and the secondharmonic signal of K-LBO is found to be 0.3 times that of KDP (Figure 6a). In comparison to LBO (3.0 × KDP), K-LBO exhibits a weak SHG response due to the partial cancellation of the contribution from the boron−oxygen groups caused by the structure rearrangement. Furthermore, from Figure 6b, the intensity of the SHG signals can be found to increase gradually when the sample size is increased, and the signals tend to be constant from 150 μm, which indicates that K-LBO is phase matchable (type I). Theoretical Calculations. In order to gain further insights into the electronic structures and optical properties of K-LBO, theoretical calculations were performed on the basis of density functional theory (DFT). As shown in Figure 7a, K-LBO shows a direct band gap of 4.90 eV which is underestimated in comparison to the experimental value; this is caused by the problem of exchange correlation using the DFT method. The total densities of states (DOS) and partial DOS for K-LBO are plotted in Figure 7b. The energy range from −5 to 0 eV at the top of the valence band contains mainly the contributions of B 2s and 2p and O 2p orbitals, indicating a possibly strong interaction between boron atoms and oxygen atoms. The part at the bottom of the conduction band contains large contributions from B 2s, H 1s, and Li 2s. As we know, the optical properties of compounds mainly come from the electronic transition between states near the Fermi energy level. Hence, the B−O groups should make a major contribution to the optical response for K-LBO, while the contributions derived from other cations such as Li+ and K+ can be ignored.

Figure 3. Experimental and calculated XRD patterns for K-LBO.

Thermal Properties. The thermogravimetric analysis (TGA) curve of K-LBO is shown in Figure 4. K-LBO exhibits

Figure 4. Thermogravimetric analysis for K-LBO.

good thermal stability and is stable up to 520 °C. K-LBO reveals two steps of weight loss stages under a nitrogen atmosphere: the first step of weight loss is due to the release of 1 mol of water per formula unit with a total weight loss of about 7.9% (calculated value 7.2%); the second step is attributed to the decomposition of the framework. Optical Properties. The IR spectrum of K-LBO is shown in Figure S1. The peaks around 3663 cm−1 can be used to confirm the presence of −OH. The band at 1352 cm−1 is the B−O asymmetric stretching vibrations in BO3 groups. The D


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Inorganic Chemistry

Figure 6. (a) SHG intensity for K-LBO with KDP as reference. (b) Phase-matching curves for K-LBO: blue triangles for K-LBO and red circles for KDP.

Figure 7. (a) Calculated band structure for K-LBO. (b) Total and partial density of states for K-LBO. (c, d) Calculated refractive indexes for LBO (c) and K-LBO (d).

layers, resulting in the enhancement of the response of electronic density distribution anisotropy,55,56 indicating that the introduction of large alkali-metal cations into classic NLO borates with a 3-D borate−oxygen cluster framework is an effective strategy to improve the birefringence.

The SHG coefficient for K-LBO was calculated to be 0.2 pm/V, in good agreement with the experimental result. As shown in Figure 7d, the refractive index dispersion curves exhibit moderate anisotropy: nx ≈ ny > nz. In comparison to its parent compound LBO (Δn = 0.040 @ 1064 nm) (Figure 7c), K-LBO displays an improved birefringence (0.064@1064 nm) which is beneficial for phase matching during the SHG process. It has been known that the macroscopic birefringence of all compounds results from the geometric addition of the microscopic anisotropic polarizabilities of the functional groups. Hence, the enlarged birefringence for K-LBO originated from the structural rearrangement of the 3-D [B3O7]5− framework in LBO to produce [B10O26]22− 2-D

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CONCLUSIONS In conclusion, new mixed-alkali-metal-containing borates ALBOs (A = K, Rb and Cs) have been obtained by introducing K+, Rb+, and Cs+ cations into the classic commercial NLO material LBO. The steric hindrance effect of the introduced large alkali-metal cations breaks the 3-D framework of [B3O 7]5− borate−oxygen clusters in LBO to produce E


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Inorganic Chemistry infrequent [B10O26]22− 2-D layers in these three title compounds, inducing an enlarged birefringence. The experimental results are confirmed by theoretical calculations, indicating that it is an effective strategy to solve the “birefringence challenge” through adjustment of the crystal structure of borates caused by introduction of large alkali-metal cations. UV−vis−NIR diffuse reflectance spectroscopy studies and SHG measurements indicate that A-LBOs (A = K, Rb, Cs) are promising deep-ultraviolet optical materials.

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natoperoxovanadate with an extremely large second-harmonic generation response. Chem. Sci. 2018, 9, 8957−8961. (8) Song, J. L.; Hu, C. L.; Xu, X.; Kong, F.; Mao, J. G. A Facile Synthetic Route to a New SHG Material with Two Types of Parallel π-Conjugated Planar Triangular Units. Angew. Chem., Int. Ed. 2015, 54, 3679−3682. (9) Ok, K. M. Toward the Rational Design of Novel Noncentrosymmetric Materials: Factors Influencing the Framework Structures. Acc. Chem. Res. 2016, 49, 2774−2785. (10) Zou, G. H.; Jo, H.; Lim, S. J.; You, T. S.; Ok, K. M. Rb3VO(O2)2CO3A Four-in-One Carbonatoperoxovanadate Exhibiting an Extremely Strong Second-Harmonic Generation Response. Angew. Chem., Int. Ed. 2018, 57, 8619−8622. (11) Zhao, S. G.; Gong, P. F.; Luo, S. Y.; Bai, L.; Lin, Z. S.; Ji, C. M.; Chen, T. L.; Hong, M. C.; Luo, J. H. Deep-Ultraviolet Transparent Phosphates RbBa2(PO3)5 and Rb2Ba3(P2O7)2 Show Nonlinear Optical Activity from Condensation of [PO4]3− Units. J. Am. Chem. Soc. 2014, 136, 8560−8563. (12) Huang, L.; Wang, Q.; Lin, C. S.; Zou, G. H.; Gao, D. J.; Bi, J.; Ye, N. Synthesis and characterization of a new beryllium-free deepultraviolet nonlinear optical material: Na2GdCO3F3. J. Alloys Compd. 2017, 724, 1057−1063. (13) Wang, Q.; He, F. F.; Huang, L.; Gao, D. J.; Bi, J.; Zou, G. H. Exploring Potential Beryllium-free, Deep-Ultraviolet Optical Crystals in the Rare Earth Fluoride Carbonate-Water System. Cryst. Growth Des. 2018, 18, 3644−3653. (14) Song, Y. X.; Luo, M.; Lin, C. S.; Ye, N. Structural Modulation of Nitrate Group with Cations to Affect SHG Responses in RE(OH)2NO3 (RE = La, Y, and Gd): New Polar Materials with Large NLO Effect after Adjusting pH Values of Reaction Systems. Chem. Mater. 2017, 29, 896−903. (15) Dong, X. H.; Huang, L.; Liu, Q. Y.; Zeng, H. M.; Lin, Z. E.; Xu, D. G.; Zou, G. H. Perfect balance harmony in Ba2NO3(OH)3a beryllium-free nitrate as a UV nonlinear optical material. Chem. Commun. 2018, 54, 5792−5795. (16) Mei, L. F.; Wang, Y.; Chen, C. T.; Wu, B. C. Nonlinear optical materials based on MBe2-BO3F2 (M = Na, K). J. Appl. Phys. 1993, 74, 7014−7015. (17) Chen, W.; Jiang, A. D.; Wang, G. F. Growth of high-quality and large-sized β-BaB2O4 crystal. J. Cryst. Growth 2003, 256, 383−386. (18) Chen, C. T.; Wu, Y. C.; Jiang, A. D.; Wu, B. C.; You, G. M.; Li, R. K.; Lin, S. J. New nonlinear-optical crystal: LiB3O5. J. Opt. Soc. Am. B 1989, 6, 616−621. (19) Li, Z. H.; Lin, Z. S.; Wu, Y. C.; Fu, P. Z.; Wang, Z. Z.; Chen, C. T. Crystal Growth, Optical Properties Measurement, and Theoretical Calculation of BPO4. Chem. Mater. 2004, 16, 2906−2908. (20) Wu, H. P.; Pan, S. L.; Poeppelmeier, K. R.; Li, H. Y.; Jia, D. Z.; Chen, Z. H.; Fan, X. Y.; Yang, Y.; Rondinelli, J. M.; Luo, H. S. K3B6O10Cl: A New Structure Analogous to Perovskite with a Large Second Harmonic Generation Response and Deep UV Absorption Edge. J. Am. Chem. Soc. 2011, 133, 7786−7790. (21) Huang, H. W.; Yao, J. Y.; Lin, Z. S.; Wang, X. Y.; He, R.; Yao, W. J.; Zhai, N. X.; Chen, C. T. NaSr3Be3B3O9F4A Promising DeepUltraviolet Nonlinear Optical Material Resulting from the Cooperative Alignment of the [Be3B3O12F]10− Anionic Group. Angew. Chem., Int. Ed. 2011, 50, 9141−9144. (22) Wu, H. P.; Yu, H. W.; Zhang, W. G.; Cantwell, J.; Poeppelmeier, K. R.; Pan, S. L.; Halasyamani, P. S. Top-Seeded Solution Crystal Growth and Linear and Nonlinear Optical Properties of Ba4B11O20F. Cryst. Growth Des. 2017, 17, 1404−1410. (23) Yu, H. W.; Zhang, W. G.; Yong, J.; Rondinelli, J. M.; Halasyamani, P. S. Design and Synthesis of the Beryllium-Free DeepUltraviolet Nonlinear Optical Material Ba3(ZnB5O10)PO4. Adv. Mater. 2015, 27, 7380−7385. (24) Halasyamani, P. S.; Zhang, W. G. Viewpoint: Inorganic Materials for UV and Deep-UV Nonlinear-Optical Applications. Inorg. Chem. 2017, 56, 12077−12085. (25) Wang, W. W.; Xu, X.; Kong, J. T.; Mao, J. G. RE(SO4)[B(OH)4](H2O), RE(SO4)[B(OH)4](H2O)2 and RE(SO4)[B(OH)4]-

ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.9b00271. Crystallographic data, IR spectrum, and EDS analysis (PDF) Accession Codes

CCDC 1883269−1883270 and 1883272 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 Authors

*E-mail for L.H.: [email protected]. *E-mail for G.Z.: [email protected]. ORCID

Ling Huang: 0000-0002-4007-5766 Daojiang Gao: 0000-0003-3600-9712 Guohong Zou: 0000-0003-4527-0058 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China (Nos. 21875146, 21501161, and 21702194).

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REFERENCES

(1) Halasyamani, P. S.; Poeppelmeier, K. R. Noncentrosymmetric Oxides. Chem. Mater. 1998, 10, 2753−2769. (2) Wickleder, M. S. Inorganic Lanthanide Compounds with Complex Anions. Chem. Rev. 2002, 102, 2011−2088. (3) Ok, K. M.; Chi, E. O.; Halasyamani, P. S. Bulk characterization methods for non-centrosymmetric materials: second-harmonic generation, piezoelectricity, pyroelectricity, and ferroelectricity. Chem. Soc. Rev. 2006, 35, 710−717. (4) Luo, M.; Liang, F.; Song, Y. X.; Zhao, D.; Xu, F.; Ye, N.; Lin, Z. S. M2B10O14F6 (M = Ca, Sr): Two Noncentrosymmetric Alkaline Earth Fluorooxoborates as Promising Next-Generation Deep-Ultraviolet Nonlinear Optical Materials. J. Am. Chem. Soc. 2018, 140, 3884−3887. (5) Shen, Y. G.; Zhao, S. G.; Luo, J. H. The role of cations in second-order nonlinear optical materials based on π-conjugated [BO3]3− groups. Coord. Chem. Rev. 2018, 366, 1−28. (6) Yu, P.; Wu, L. M.; Zhou, L. J.; Chen, L. Deep-Ultraviolet Nonlinear Optical Crystals: Ba3P3O10X (X = Cl, Br). J. Am. Chem. Soc. 2014, 136, 480−487. (7) Zou, G. H.; Lin, Z. E.; Zeng, H. M.; Jo, H.; Lim, S. J.; You, T. S.; Ok, K. M. Cs3VO(O2)2CO3 an exceptionally thermostable carboF


Article

Inorganic Chemistry (H2O)·H2O: Rare-Earth Borate-Sulfates Featuring Three Types of Layered Structures. Inorg. Chem. 2018, 57, 163−174. (26) He, F. F.; Wang, Q.; Hu, C. F.; He, W.; Luo, X. Y.; Huang, L.; Gao, D. J.; Bi, J.; Wan, X.; Zou, G. H. Centrosymmetric (NH4)2SbCl(SO4)2 and Non-centrosymmetric (NH4)SbCl2(SO4): Synergistic Effect of Hydrogen-Bonding Interactions and Lone-Pair Cations on the Framework Structures and Macroscopic Centricities. Cryst. Growth Des. 2018, 18, 6239−6247. (27) Huang, L.; Wang, Q.; He, F. F.; Liu, X. Y.; Chen, Z. W.; He, W.; Luo, X. Y.; Gao, D. J.; Bi, J.; Zou, G. H. Synthesis, crystal structures and nonlinear optical properties of polymorphism: α- and β-RbHgI3·H2O. J. Alloys Compd. 2019, 771, 547−554. (28) Zou, G. H.; Huang, L.; Ye, N.; Lin, C. S.; Cheng, W. D.; Huang, H. CsPbCO3F: A Strong Second-Harmonic Generation Material Derived from Enhancement via p-π Interaction. J. Am. Chem. Soc. 2013, 135, 18560−18566. (29) Huang, L.; Zou, G. H.; Cai, H. Q.; Wang, S. C.; Lin, C. S.; Ye, N. Sr2(OH)3NO3 the first nitrate as a deep UV nonlinear optical material with large SHG responses. J. Mater. Chem. C 2015, 3, 5268− 5274. (30) Chen, J.; Xiong, L.; Chen, L.; Wu, L. M. Ba2NaClP2O7Unprecedented Phase Matchability Induced by Symmetry Breaking and Its Unique Fresnoite-Type Structure. J. Am. Chem. Soc. 2018, 140, 14082−14086. (31) Cheng, L.; Yang, G. Y. A novel aluminoborate open-framework [In(dien)2][Al2B7O16H2] with large chiral cavities templated by chiral main group metal complexes. Chem. Commun. 2014, 50, 344−346. (32) Wei, L.; Wei, Q.; Lin, Z. E.; Meng, Q.; He, H.; Yang, B. F.; Yang, G. Y. A 3DAluminoborate Open Framework Interpenetrated by 2D Zinc-Amine Coordination-Polymer Networks in Its 11-Ring Channels. Angew. Chem., Int. Ed. 2014, 53, 7188−7191. (33) Yang, G. S.; Gong, P. F.; Lin, Z. S.; Ye, N. AZn2BO3X2(A = K, Rb, NH4X = Cl, Br): New Members of KBBF Family Exhibiting Large SHG Response and the Enhancement of Layer Interaction by Modified Structures. Chem. Mater. 2016, 28, 9122−9131. (34) Yu, H. W.; Wu, H. P.; Pan, S. L.; Yang, Z. H.; Hou, X. L.; Su, X.; Jing, Q.; Poeppelmeier, K. R.; Rondinelli, J. M. Cs3Zn6B9O21A Chemically Benign Member of the KBBF Family Exhibiting the Largest Second Harmonic Generation Response. J. Am. Chem. Soc. 2014, 136, 1264−1267. (35) Zhao, S. G.; Gong, P. F.; Luo, S. Y.; Liu, S. J.; Li, L. N.; Asghar, M. A.; Khan, T.; Hong, M. C.; Lin, Z. S.; Luo, J. H. Beryllium-Free Rb3Al3B3O10F with Reinforced Interlayer Bonding as a DeepUltraviolet Nonlinear Optical Crystal. J. Am. Chem. Soc. 2015, 137, 2207−2210. (36) Huang, H. W.; Yao, J. Y.; Lin, Z. S.; Wang, X. Y.; He, R.; Yao, W. J.; Zhai, N. X.; Chen, C. T. Molecular Engineering Design to Resolve the Layering Habit and Polymorphism Problems in Deep UV NLO Crystals: New Structures in MM′Be2B2O6F (M = Na, M′=Ca; M = K, M′=Ca, Sr). Chem. Mater. 2011, 23, 5457−5463. (37) Wu, H. P.; Yu, H. W.; Pan, S. L.; Halasyamani, P. S. DeepUltraviolet Nonlinear-Optical Material K3Sr3Li2Al4B6O20F: Addressing the Structural Instability Problem in KBe2BO3F2. Inorg. Chem. 2017, 56, 8755−8758. (38) Zhao, B. Q.; Li, B. X.; Zhao, S. G.; Liu, X. T.; Wu, Z. Y.; Shen, Y. G.; Li, X. F.; Ding, Q. R.; Ji, C. M.; Luo, J. H. Physical Properties of a Promising Nonlinear Optical Crystal K3Ba3Li2Al4B6O20F. Cryst. Growth Des. 2018, 18, 7368−7372. (39) Chen, C.; Wang, Y.; Wu, B.; Wu, K.; Zeng, W.; Yu, L. Design and synthesis of an ultraviolet-transparent nonlinear optical crystal Sr2Be2B2O7. Nature 1995, 373, 322−324. (40) Wang, Y.; Zhang, B. B.; Yang, Z. H.; Pan, S. L. Cation-Tuned Synthesis of Fluorooxoborates: Towards Optimal Deep-Ultraviolet Nonlinear Optical Materials. Angew. Chem. 2018, 130, 2172−2176. (41) Zhang, Z. Z.; Wang, Y.; Zhang, B. B.; Yang, Z. H.; Pan, S. L. Polar Fluorooxoborate, NaB4O6F: A Promising Material for Ionic Conduction and Nonlinear Optics. Angew. Chem., Int. Ed. 2018, 57, 6577−6581.

(42) Mutailipu, M.; Zhang, M.; Zhang, B. B.; Wang, L. Y.; Yang, Z. H.; Zhou, X.; Pan, S. L. SrB5O7F3 Functionalized with [B5O9F3]6− Chromophores: Accelerating the Rational Design of Deep Ultraviolet Nonlinear Optical Materials. Angew. Chem., Int. Ed. 2018, 57, 6095− 6099. (43) Sheldrick, G. M. SHELXL-97, Program for crystal structure refinement; University of Göttingen: Göttingen, Germany, 1997. (44) Sheldrick, G. M. A short history of SHELX. Acta Crystallogr., Sect. A: Found. Crystallogr. 2008, 64, 112−122. (45) Wang, J. P.; Duan, X. Y.; Du, X. D.; Niu, J. Y. Novel Rare Earth Germanotungstates and Organic Hybrid Derivatives: Synthesis and Structures of M/[α-GeW11O39] (M = Nd, Sm, Y, Yb) and Sm/[αGeW11O39](DMSO). Cryst. Growth Des. 2006, 6, 2266−2270. (46) Han, S. J.; Wang, Y.; Zhang, B. B.; Yang, Z. H.; Pan, S. L. A Member of Fluorooxoborates: Li2Na0.9K0.1B5O8F2 with the Fundamental Building Block B5O10F2 and a Short Cutoff Edge. Inorg. Chem. 2018, 57, 873−878. (47) Zhang, J.; Xue, Y. S.; Liang, L. L.; Ren, S. B.; Li, Y. Z.; Du, H. B.; You, X. Z. Porous Coordination Polymers of Transition Metal Sulfides with PtS Topology Built on a Semirigid Tetrahedral Linker. Inorg. Chem. 2010, 49, 7685−7691. (48) Spek, A. L. Single-crystal structure validation with the program PLATON. J. Appl. Crystallogr. 2003, 36, 7−13. (49) Kurtz, S. K.; Perry, T. T. A powder technique for the evaluation of nonlinear optical materials. J. Appl. Phys. 1968, 39, 3798−3813. (50) Segall, M. D.; Philip, J. D.; Probert, M. J.; Pickard, C. J.; Hasnip, P. J.; Clark, S. J.; Payne, M. C. First-principles simulation: ideas, illustrations and the CASTEP code. J. Phys.: Condens. Matter 2002, 14, 2717. (51) Perdew, J. P.; Burke, K.; Ernzerhof, M. Generalized Gradient Approximation Made Simple. Phys. Rev. Lett. 1996, 77, 3865. (52) Burns, P. C.; Grice, J. D.; Hawthorne, F. C. Borate minerals. Ι. polyhedral clusters and fundamental building blocks. Can. Mineral. 1995, 33, 1131−1151. (53) Wang, Q.; Lin, C. S.; Zou, G. H.; Liu, M. J.; Gao, D. J.; Bi, J.; Huang, L. K2[B3O3(OH)5]: A new deep-UV nonlinear optical crystal with isolated [B3O3(OH)5]2− anionic groups. J. Alloys Compd. 2018, 735, 677−683. (54) Zou, G. H.; Lin, C. S.; Jo, H.; Nam, G.; You, T. S.; Ok, K. M. Pb2BO3Cl: A Tailor-Made Polar Lead Borate Chloride with Very Strong Second Harmonic Generation. Angew. Chem. 2016, 128, 12257−12261. (55) Dong, X. H.; Huang, L.; Hu, C. F.; Zeng, H. M.; Lin, Z. E.; Wang, X.; Ok, K. M.; Zou, G. H. CsSbF2SO4: An Excellent Ultraviolet Nonlinear Optical Sulfate with a KTiOPO4(KTP) Type Structure. Angew. Chem., Int. Ed. 2019, DOI: 10.1002/anie.201900637. (56) Lei, B. H.; Yang, Z. H.; Pan, S. L. Enhancing optical anisotropy of crystals by optimizing bonding electron distribution in anionic groups. Chem. Commun. 2017, 53, 2818−2821.

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