Article Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX
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LiNa4B15O25: Featuring Unprecedented B15O30 Fundamental Building Block and Deep-UV Cutoff Edge Yun Yang,‡ Qingrong Kong,‡ Zhihua Yang, and Shilie Pan* CAS Key Laboratory of Functional Materials and Devices for Special Environments; Xinjiang Technical Institute of Physics & Chemistry, CAS; Xinjiang Key Laboratory of Electronic Information Materials and Devices, 40-1 South Beijing Road, Urumqi 830011, China S Supporting Information *
ABSTRACT: In the Li2O−Na2O−B2O3 system, LiNa4B15O25 has been successfully synthesized, which crystallizes in monoclinic space group C2/c (No. 15), a = 14.153(3) Å, b = 12.122(2) Å, c = 12.719(2) Å, β = 105.237(13)°, and Z = 4. The isolated LiO5 polyhedra and the Na4O18 tetramers are located in the void space of the 3D ∞[B15O25] network of LiNa4B15O25. The symmetry of B15O30 is a new fundamental building block, which has never been reported before. Moreover, the whole framework can be defined as a new topology based on the TOPOS database. Interestingly, for the crystal structure LiB3O5, as 4/5 Li+ ions are substituted by the Na+ ions, a new compound LiNa4B15O25 has been successfully prepared. The structural comparison between the structures of LiB3O5 and LiNa4B15O25 and the changes caused by the cation substitution are discussed in this paper.
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INTRODUCTION The excellent performances of materials are often governed by crystal structures. Borates have attracted a respectable amount of interest due to the variably flexible structures and outstanding application abilities in many fields such as nonlinear optical materials, etc.1−15 In view of the relationship between crystal structures and properties, the flexible B-O units lead to the multifunction of borates and excellent performance.16−19 For boron, the outer electronic structure is 2s22p1, so the hybridized atomic orbitals types are sp2 or sp3. Therefore, the boron atom can coordinate with oxygen atoms to form BO3 or BO4. Then the BO3 triangles or the BO4 tetrahedra can share edges or corners to construct various B-O fundamental building blocks (FBBs), e.g., B2O5, B3O6, B3O7, B5O10, B7O14, etc.20−27 Therefore, the topologies of the open frameworks obviously can be enormously enriched by the geometric flexibility of boron atoms. Until now, one of the major challenges in this area is how to design and synthesize optical materials with good properties. The B-rich system with a large boron proportion is propitious to eliminate the terminal O atoms of the B-O units. Accordingly, it is expected to explore more borates which can be applied in the ultraviolet (UV) or deep-UV region28−30 and then improve the laser-damage thresholds. And also, because of no d−d or f−f electron transitions, the introduction of alkaline metals can effectively shorten the cutoff edge to the UV or even deep-UV region. The typical materials are LiB3O5 (LBO),31 CsB3O5 (CBO),32 and CsLiB6O10 (CLBO),33,34 etc. Therefore, a method for designing crystals with deep-UV properties is to combine B-rich (FBBs) with alkali-metal ions, which can lead © XXXX American Chemical Society
to discover the desired UV or deep-UV optical crystals with intriguing structures and interesting properties. In Pan’s group, we have been particularly interested in the rational synthesis of borate networks for optical applications. Several B-rich alkalimetal borates have been reported, such as Na8MB21O36 (M = Rb and Cs),35 K2BaB16O26, Na2M2NB18O30 (M = Rb, Cs; N = Ba, Pb), and K3CsB20O32,36 Na2M2B20O32 (M = Rb, Cs),37 Li4Cs4B40O64,37 M2Ca3B16O28 (M = Rb, Cs),38 etc. One of the interesting features of these compounds is the short wavelength absorption, which attracts us to continue research in alkalimetal B-rich borates systematically. In the alkali metal borates system, the famous LiB3O5 displays the infinite anti-helical arrangement chains built by the B3O7 rings, which presents one of the shortest cutoff wavelengths of all the known nonlinear optical metal borate crystals. In crystal engineering, one of the efficient and most important methods to create novel crystals with excellent optical properties is modification of the crystal structure by appropriately varying the cationic subsystem.39−47 More compounds are expected to be prepared which can retain the advantages of the structure and display excellent properties like LiB3O5 through cation substitution. Inspired by the above idea, alkali metal borate systems are still being locked as research targets. For the crystal structure of LiB3O5, 4/5 Li+ ions are substituted by the Na+ ions and then a new compound LiNa4B15O25 is obtained. Through extensive research on the Li2O−Na2O−B2O3 system, LiNa4B15O25 has been successfully Received: January 1, 2018
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DOI: 10.1021/acs.inorgchem.7b03243 Inorg. Chem. XXXX, XXX, XXX−XXX
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Inorganic Chemistry Table 1. Crystal Data and Structure Refinement Information empirical formula formula weight temperature (K) crystal system crystal size, mm3 space group, Z a (Å) b (Å) c (Å) β (deg) volume (Å3) density (calcd, g/cm3) absorption coefficient (mm−1) F(000) index ranges reflections collected/unique data/restraints/parameters goodness-of-fit on F2 final R indices [Fo2 > 2σ(Fo2)]a R indices (all data)a extinction coefficient largest diff. peak and hole (e·Å−3) a
LiNa4B15O25 661.05 296(2) monoclinic 0.128 × 0.109 × 0.097 C2/c, 4 14.153(3) 12.122(2) 12.719(2) 105.237(13) 2105.4(7) 2.086 0.262 1288 −11 ≤ h ≤ 18, −15 ≤ k ≤ 15, −16 ≤ l ≤ 16 9258/2407 [R(int) = 0.0473] 2407/0/206 1.088 R1 = 0.0417, wR2 = 0.1008 R1 = 0.0631, wR2 = 0.1116 0.0015(6) 0.418 and −0.539
R1 = ∑||Fo| − |Fc||/∑|Fo| and wR2 = [∑w(Fo2 − Fc2)2/∑wFo4]1/2 for Fo2 > 2σ(Fo2). X-ray Crystallographic Studies. Single-crystal X-ray diffraction data for LiNa4B15O25 were collected at 296(2) K on the Bruker Smart APEX II single-crystal diffractometer with Mo Kα radiation (λ = 0.71073 Å). SHELXS48 was used to solve structures by direct methods,49 and SHELXL was used to refine data by full matrix leastsquares methods.50 The missing symmetry elements were checked by PLATON.51 In Table 1, crystallographic data are summarized. The lists for atomic coordinates, equivalent isotropic displacement parameters (Å2), and bond valence sum (BVS) for LiNa4B15O25 are presented in Table S1 in the SI. In Table S2 in the SI, a part of the important bond lengths and bond angles are shown. Thermal Analysis. The thermal property measurement was carried out on a NETZSCH STA 449C thermal analyzer instrument. The rate of heating was about 10 °C/min in flowing nitrogen from the temperature of about 25 to 1200 °C. Spectroscopic Measurements. The UV−vis−NIR diffusereflectance behavior of LiNa4B15O25 was studied using a SolidSpec3700DUV spectrophotometer within the range of about 190−2600 nm. The reflectance (R) data were converted to absorbance by the Kubelka−Munk function [F(R) = (1 − R)2/2R].52,53 The IR spectrum was recorded on a Shimadzu IR Affinity-11 Fourier transform infrared spectrometer within the range of about 400−4000 cm−1 using the pellet prepared by the sample mixed with KBr. Theoretical Calculations. The DFT method implemented in the CASTEP module performs the electronic structures and optical properties of LiNa4B15O25.54−59 The valence electron configurations for diverse electron orbital pseudopotentials are Li 2s1, Na 2s22p63s1, B 2s22p1, and O 2s22p4. Other computing conditions are similar to those of previous publications.35−38
prepared, which exhibits a novel anionic framework structure. It demonstrates that the cation substitution has an evident influence on the alkali-metal borates architectures and in fact modulates the crystal structures and the performance of the material can be further affected. A topological approach is applied in order to simplify the 3D architecture. In addition, characterization, including optical properties analysis, thermal analysis, and first principles calculations of LiNa4B15O25 are presented in this paper.
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EXPERIMENTAL SECTION
Synthesis. The synthesis procedure is as follows: LiNa4B15O25 was prepared by high-temperature reaction in air. Li2CO3, Na2CO3, and B2O3 were mixed thoroughly with a stoichiometric ratio. The preparation process can be represented as the following chemical equation:
Li 2CO3 + 4Na 2CO3 + 15B2O3 → 2LiNa4B15O25 + 5CO2 ↑ First, the sample was heated at 400 °C for about 12 h, so carbonate can be decomposed. After that, it was kept at about 650 °C for 48 h with several mixing and grinding. The polycrystalline sample was investigated by powder X-ray diffraction (pXRD) analyses. In Figure S1 in the SI, the experimental pXRD pattern of LiNa4B15O25 matches the calculated one which is exported from the single-crystal structure data. The LiNa4B15O25 crystals were synthesized from a reaction containing 0.65 g of LiF, 0.925 g of Li2CO3, 1.05 g of NaF, 2.65 g of Na2CO3, and 13.12 g of B2O3 (the LiF/Li2CO3/NaF/Na2CO3/ B2O3 molar ratio = 2:1:2:2:15) by the high-temperature solution method. Chemical reagents above were mixed and ground thoroughly. First, the mixed powder was heated to 770 °C and held for 10 h in a platinum crucible, so the solution can be ensured homogeneous. Then the solution was cooled down to 640 °C at 2 °C/h, and the block and colorless crystals can be seen on the solution surface. Finally, it was cooled down to room temperature. The small high quality crystals were obtained as crystal structure characterization. Powder X-ray Diffraction. The Bruker D2 PHASER diffractometer was used to measure the pXRD patterns of polycrystalline with Cu Kα radiation (λ = 1.5418 Å). The range of 2θ was 10−70° with 0.02°/steps. The measurement was done at room temperature.
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RESULTS AND DISCUSSION Structural Description. For the LiNa4B15O25 crystal structure, in the monoclinic space group C2/c, the Li(1) atom is defined by the O atoms forming the Li(1)O5 polyhedron. The bond lengths of Li−O are from 1.984(16) to 2.115(6) Å. For Na(1), a distorted octahedron NaO6 is formed by the Na(1) and six O atoms with the Na−O bonds from 2.3145(18) to 2.8068(19) Å. Na(2) is bonded to five O atoms with bond lengths of Na−O ranging from 2.293(2) to B
DOI: 10.1021/acs.inorgchem.7b03243 Inorg. Chem. XXXX, XXX, XXX−XXX
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Figure 1. The crystal structure of LiNa4B15O25. (a) The B15O30 fundamental building block. (b) The infinite B−O ring chain. (c) The B3O7 rings. (d) The whole structure along the c axis.
the 1D infinite anti-helix B−O chains first. And then the chains are bridged by corner-sharing oxygen atoms to build the 3D framework. As described above, for LiNa4B15O25, the basic FBB B15O30 is composed of five B3O7 polymerization clusters. And the [B15O25]∞ 3D framework is constituted by the further connected B15O30 groups. Second, in order to investigate the structure assembly with complex frameworks, the structure of LiNa 4 B 15 O 25 is topological when the B3O7 ring is considered as four-connected (4c) nodes. The topology framework could be described as {4.62.83}{42.62.82}2{44.62}2 (Figure 2) according to the Schläfli symbol. On the basis of the TOPOS database, it defines a new topology69 and it can be further confirmed as a new structural type of borates. We discuss the versatile structure derivation via the flexible assembly of B-O units comparing with LiB3O5. In LiB3O5, the B3O7 rings connect to build 1D infinite anti-helix B−O chains (Figure 3a). In LiNa4B15O25, the FBB B15O30 has
2.568(2) Å (Table S2 in the SI). The Na2O10 units were formed by Na(1)O6 and Na(2)O5 via sharing O(6) atoms. Two Na2O10 units are bridged by two O(10) atoms to form isolated Na4O18 tetramers (Figure S2 in the SI). According to the Inorganic Crystal Structure Database (ICSD) and recently published literature, there is only the Na2B4O6(OH)2(H2O)3 compound containing Na4O18 tetramers.60 In terms of the B atoms, three/four O atoms contribute to the formation of BO3 or BO4. The B−O bond lengths and angles of BO3 and BO4 are in good agreement with other borate compounds reported previously (Table S2 in the SI).35−38,61−64 And then BO3 and BO4 link together to form the classic B3O7 clusters. Via sharing oxygen atoms, five B3O7 polymerization clusters compose the basic FBB B15O30 (Figure 1a) which can be written as 15:[15:10Δ + 5T].65,66 As far as we know, the symmetry of B15O30 is a new FBB, which has never been reported. In Figure 1d, we can see that the B15O30 group can be divided into two parts: one part is made up of one B3O7 ring (two B(3), and B(8)) (Figure 1c); the other part is made up of four B3O7 rings via sharing edges and two O(6) atoms to form infinite B−O ring chains (Figure 1b). The infinite B−O ring chains are further connected with each other by the B3O7 ring to constitute the [B15O25]∞ 3D network. The isolated LiO5 polyhedra and short isolated Na4O18 tetramers are placed in the cavities of the 3D [B15O25]∞ network (Figure 1d) to build the whole 3D framework. The bond valences have been calculated to check the consistency of the structure determination.67,68 And the results for the calculated total bond valences of Li, Na, B agree with the expected oxidation states (Table S1 in the SI). Effect of Ions Substitution on Structural Transition. Interestingly, for LiB3O5, as 4/5 Li+ are replaced by Na+, LiNa4B15O25 is obtained. Both of the two structures adopt the same B3O7 rings, but present different crystal configurations. First, the connection mode between the B3O7 rings is very different. In the asymmetric unit of LiB3O5, the B3O7 rings form
Figure 2. The 4-nodal topological network (the Schläfli symbol: {4.62.83}{42.62.82}2{44.62}2). C
DOI: 10.1021/acs.inorgchem.7b03243 Inorg. Chem. XXXX, XXX, XXX−XXX
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Figure 3. (a) The B-O 3D network of LiB3O5 with infinite helix chain. (b) The topology of the B-O 3D structure of LiNa4B15O25 along the c axis with an infinite Z chain.
standpoint of large size crystal growth, the congruent melting compound can be grown rapidly from the melt. And it is very effective in preventing bringing impurities into crystal in the process of crystal growth. Optical Analysis. The assignments for the IR absorption peaks (Figure S3 in the SI) can be presented as follows: The main IR absorption region at 1397−1285 cm−1 is owing to asymmetric stretching of the BO3 groups. The absorptions at 1116, 867, and 769 cm−1 correspond to asymmetry and symmetry stretching of the BO4 groups. The band at 978 cm−1 is due to symmetry stretching of the BO3 groups. The out-ofplane bending of BO3 is given at 693 cm−1. And the weak band at 533 cm−1 shows the bending modes of the BO3 and BO4 groups. In this IR spectrum, the absorption peaks observed are in agreement with the ones obtained from other borates.61−64 For single crystals applications, the UV cutoff edge and the optical transmission range are very important. The cutoff edge is below 190 nm (Figure 5). And in the range of 190−2600 nm, no obvious absorption peak presents in the UV−vis−NIR diffuse reflectance spectrum. Figure 6 shows that its indirect band gap is 5.04 eV, which agrees with the experimental one, 6.2 eV. To eliminate the determination of the optical gaps in the view of the electronic structure, the band gap and density of
four terminal O atoms with similar distribution and arranges like an infinite Z chain along the c axis (Figure 3b). Third, the affection originates from the different sizes of Na+ and Li+. In LiNa4B15O25, the Na atoms have two different coordination environments, Na(1)O6 and Na(2)O5; they form isolated Na4O18 tetramers. For LiB3O5, the cations have only one coordination environment, LiO4. That means, the original space environment of the cation is destroyed, when Li+ is replaced by the introduced larger Na+, which leads to create an overall centric structure. Thermal Analysis. In the DSC heating curve in Figure 4, there is only one endothermic peak at 786 °C. And the thermal
Figure 4. TG−DSC curves of LiNa4B15O25.
behavior of the compound needs further confirmation. The sample of LiNa4B15O25 is heated up to 850 °C to melt completely in a platinum crucible. Then it is slowly cooled to room temperature. The pXRD pattern is used to analyze the residue. It reveals that the melted solid product shows a pXRD pattern being coincident with that of the LiNa4B 15 O 25 polycrystalline (Figure S1 in the SI), which demonstrates that LiNa4B15O25 is a congruent melting compound. From the
Figure 5. UV−vis−NIR diffuse reflectance spectrum of LiNa4B15O25. D
DOI: 10.1021/acs.inorgchem.7b03243 Inorg. Chem. XXXX, XXX, XXX−XXX
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polyhedra and the Na4O18 tetramers. Its FBB is the B15O30 group, which is a new FBB and has never been reported before. Moreover, the whole framework defines a new topology, so the structure is a new type of borates. The UV cutoff edge is below 190 nm, which indicates that linking alkali-metal ions with Brich functional building blocks (FBBs) is an effective strategy for the design of new desired UV or deep-UV optical compounds. And for the congruent melting LiNa4B15O25 compound, it can be very effective in preventing bringing impurities into the crystal in the process of crystal growth.
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ASSOCIATED CONTENT
S Supporting Information *
Figure 6. Calculated band structure of LiNa4B15O25.
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.7b03243. Table of crystal information, atomic coordinates, bond valence sum, and infrared spectrum of LiNa4B15O25 (PDF)
states (DOS) of LiNa4B15O25 were calculated by the density functional theory (DFT) calculation. The DOS of LiNa4B15O25 is demonstrated in Figure 7, from which we can get the
Accession Codes
CCDC 1481425 contains 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 data_
[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
*E-mail:
[email protected]. ORCID
Shilie Pan: 0000-0003-4521-4507 Author Contributions ‡
These authors contributed equally.
Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS This work was supported by the Xinjiang Key Laboratory Foundation (Grant No. 2014KL009), the 973 Program of China (Grant No. 2014CB648400), the National Natural Science Foundation of China (Grant Nos. U1703132, 51425206, 91622107), and the Science and Technology Project of Urumqi (Grant No. P161010002).
Figure 7. Total and partial densities of states of LiNa4B15O25.
respective contributions of atoms in the near Fermi surface. In the conduction bands, the contributions mainly come from hybridization orbitals from B-O. The dominating states are from the 2p orbital of O2− at the top of valence bands. Generally speaking, O-nonbonding p orbitals and the hybridization orbitals of B-O control the near Fermi level, which is the universal electronic character for alkali borates.70 Considering the crystal structure, the high transparency of LiNa4B15O25 can be explained as follows: First, alkaline metals without electron transitions of d−d or f−f can effectively shorten the cutoff edge even to the UV or deep-UV region. Second, the B-rich FBB B15O30 with a large boron proportion is propitious to eliminate the terminal O atoms of the B-O units, which leads to a large band gap making it suitable for the UV region. This is very effective for the design of new compounds applied in the UV region.
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REFERENCES
(1) Chen, C. T.; Lu, J. H.; Togashi, T.; Suganuma, T.; Sekikawa, T.; Watanabe, S.; Xu, Z. Y.; Wang, J. Y. Second-harmonic generation from a KBe2BO3F2 crystal in the deep ultraviolet. Opt. Lett. 2002, 27, 637− 639. (2) Wu, H. P.; Yu, H. W.; Yang, Z. H.; Hou, X. L.; Pan, S. L.; Su, X.; Poeppelmeier, K. R.; Rondinelli, J. M. Designing a deep ultraviolet nonlinear optical material with large second harmonic generation response. J. Am. Chem. Soc. 2013, 135, 4215−4218. (3) Zhang, B. B.; Shi, G. Q.; Yang, Z. H.; Zhang, F. F.; Pan, S. L. Fluorooxoborates: Beryllium-free deep-ultraviolet nonlinear optical materials without layered growth. Angew. Chem., Int. Ed. 2017, 56, 3916−3919. (4) Wang, X. F.; Wang, Y.; Zhang, B. B.; Zhang, F. F.; Yang, Z. H.; Pan, S. L. CsB4O6F: A congruent-melting deep-ultraviolet nonlinear optical material by combining superior functional units. Angew. Chem., Int. Ed. 2017, 56, 14119−14123.
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CONCLUSION In summary, a new congruent melting compound LiNa4B15O25 has been discovered. The complicated 3D [B15O25]∞ network includes void space which is occupied by isolated LiO5 E
DOI: 10.1021/acs.inorgchem.7b03243 Inorg. Chem. XXXX, XXX, XXX−XXX
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Inorganic Chemistry (5) Becker, P. Borate materials in nonlinear optics. Adv. Mater. 1998, 10, 979−992. (6) Halasyamani, P. S.; Poeppelmeier, K. R. Noncentrosymmetric oxides. Chem. Mater. 1998, 10, 2753−2769. (7) Jin, S. F.; Cai, G. M.; Wang, W. Y.; He, M.; Wang, S. C.; Chen, X. L. Stable oxoborate with edge-sharing BO4 tetrahedra synthesized under ambient pressure. Angew. Chem., Int. Ed. 2010, 49, 4967−4970. (8) Yuan, G. H.; Xue, D. F. Crystal chemistry of borates: The classification and algebraic description by topological type of fundamental building blocks. Acta Crystallogr., Sect. B: Struct. Sci. 2007, 63, 353−362. (9) Zhang, G. C.; Liu, Z. L.; Zhang, J. X.; Fan, F. D.; Liu, Y. C.; Fu, P. Z. Crystal growth, structure, and properties of a non-centrosymmetric fluoride borate, Ba3Sr4(BO3)3F5. Cryst. Growth Des. 2009, 9, 3137− 3141. (10) Li, R. K.; Yu, Y. Ba4Ga2B8O18Cl2·NaCl: A new polar structure with NaCl inclusion. Inorg. Chem. 2006, 45, 6840−6843. (11) Song, J. L.; Hu, C. L.; Xu, X.; Kong, F.; Mao, J. G. Pb2B3O5.5(OH)2 and [Pb3(B3O7)](NO3): Facile syntheses of new Lead(II) borates by simply changing the pH values of the reaction systems. Inorg. Chem. 2013, 52, 8979−8986. (12) Wang, S. C.; Ye, N.; Li, W.; Zhao, D. Alkaline beryllium borate NaBeB3O6 and ABe2B3O7 (A = K, Rb) as UV nonlinear optical crystals. J. Am. Chem. Soc. 2010, 132, 8779−8786. (13) Chang, H. Y.; Kim, S. H.; Ok, K. M.; Halasyamani, P. S. Polar or nonpolar? A+ cation polarity control in A2Ti(IO3)6 (A = Li, Na, K, Rb, Cs, Tl). J. Am. Chem. Soc. 2009, 131, 6865−6873. (14) Rong, C.; Yu, Z. W.; Wang, Q.; Zheng, S. T.; Pan, C. Y.; Deng, F.; Yang, G. Y. Aluminoborates with open frameworks: Syntheses, structures, and properties. Inorg. Chem. 2009, 48, 3650−3659. (15) Chen, X. A.; Li, M.; Chang, X. A.; Zang, H. G.; Xiao, W. Q. Synthesis and crystal structure of a novel pentaborate, Na3ZnB5O10. J. Solid State Chem. 2007, 180, 1658−1663. (16) Huang, H. W.; Liu, L. J.; Jin, S. F.; Yao, W. J.; Zhang, Y. H.; Chen, C. T. Deep-ultraviolet nonlinear optical materials: Na2Be4B4O11 and LiNa5Be12B12O33. J. Am. Chem. Soc. 2013, 135, 18319−18322. (17) Kong, F.; Huang, S. P.; Sun, Z. M.; Mao, J. G.; Cheng, W. D. Se2(B2O7): A new type of second-order NLO material. J. Am. Chem. Soc. 2006, 128, 7750−7751. (18) Xu, X.; Hu, C. L.; Kong, F.; Zhang, J. H.; Mao, J. G. Ca10Ge16B6O51 and Cd12Ge17B8O58: Two types of new 3D frameworks based on BO4 tetrahedra and 1D [Ge4O12]n Chains. Inorg. Chem. 2011, 50, 8861−8868. (19) 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 deep-ultraviolet nonlinear optical crystal. J. Am. Chem. Soc. 2015, 137, 2207−2210. (20) Christ, C. L.; Clark, J. R. A crystal-chemical classification of borate structures with emphasis on hydrated borates. Phys. Chem. Miner. 1977, 2, 59−87. (21) Keszler, D. A.; Akella, A.; Schaffers, K. I.; Alekel, T. New borate structures for NLO applications. MRS Online Proc. Libr. 1993, 329, 15−22. (22) Huang, H. W.; Yao, J. Y.; Lin, Z. H.; Wang, X. Y.; He, R.; Yao, W. J.; Zhai, N. X.; Chen, C. T. NaSr3Be3B3O9F4: A promising deepultraviolet nonlinear optical material resulting from the cooperative alignment of the [Be3B3O12F]10− anionic group. Angew. Chem., Int. Ed. 2011, 50, 9141−9144. (23) Chen, C. T.; Luo, S. Y.; Wang, X. Y.; Wang, G. L.; Wen, X. H.; Wu, H. X.; Zhang, X.; Xu, Z. Y. Deep UV nonlinear optical crystal: RbBe2(BO3)F2. J. Opt. Soc. Am. B 2009, 26, 1519−1525. (24) Xue, D. F.; Betzler, K.; Hesse, H. Chemical-bond analysis of the nonlinear optical properties of the borate crystals LiB3O5, CsLiB6O10, and CsB3O5. Appl. Phys. A: Mater. Sci. Process. 2002, 74, 779−782. (25) Wang, S. C.; Ye, N. Na2CsBe6B5O15: An alkaline beryllium borate as a deep-UV nonlinear optical crystal. J. Am. Chem. Soc. 2011, 133, 11458−11461.
(26) Belokoneva, E. L. Borate crystal chemistry in terms of the extended OD theory: Topology and symmetry analysis. Crystallogr. Rev. 2005, 11, 151−198. (27) Touboul, M.; Penin, N.; Nowogrocki, G. Borates: A survey of main trends concerning crystal-chemistry, polymorphism and dehydration process of alkaline and pseudo-alkaline borates. Solid State Sci. 2003, 5, 1327−1342. (28) Jiang, X. X.; Molokeev, M. S.; Gong, P. F.; Yang, Y.; Wang, W.; Wang, S. H.; Wu, S. F.; Wang, Y. X.; Huang, R. J.; Li, L. F.; Wu, Y. C.; Xing, X. R.; Lin, Z. S. Near-zero thermal expansion and high ultraviolet transparency in a borate crystal of Zn4B6O13. Adv. Mater. 2016, 28, 7936−7940. (29) Jiang, X. X.; Luo, S. Y.; Kang, L.; Gong, P. F.; Yao, W. J.; Huang, H. W.; Li, W.; Huang, R. J.; Wang, W.; Li, Y. C.; Li, X. D.; Wu, X.; Lu, P. X.; Li, L. F.; Chen, C. T.; Lin, Z. S. Isotropic negative area compressibility over large pressure range in potassium beryllium fluoroborate and its potential applications in deep ultraviolet region. Adv. Mater. 2015, 27, 4851−4857. (30) Kang, L.; Jiang, X.; Luo, S.; Gong, P.; Li, W.; Wu, X.; Li, Y. C.; Li, X. D.; Chen, C. T.; Lin, Z. S. Negative linear compressibility in a crystal of α-BiB3O6. Sci. Rep. 2015, 5, 13432−13438. (31) 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. (32) Wu, Y. C.; Sasaki, T.; Nakai, S.; Yokotani, A.; Tang, H.; Chen, C. T. CsB3O5: A new nonlinear optical crystal. Appl. Phys. Lett. 1993, 62, 2614−2615. (33) Mori, Y.; Kuroda, I.; Nakajima, S.; Sasaki, T.; Nakai, S. New nonlinear optical crystal: Cesium lithium borate. Appl. Phys. Lett. 1995, 67, 1818−1820. (34) Tu, J. M.; Keszler, D. A. CsLiB6O10: A noncentrosymmetric polyborate. Mater. Res. Bull. 1995, 30, 209−215. (35) Mutailipu, M.; Zhang, M.; Su, X.; Yang, Z. H.; Pan, S. L. Na8MB21O36 (M = Rb and Cs): Noncentrosymmetric borates with unprecedented [B21O36]9− fundamental building blocks. Inorg. Chem. 2017, 56, 5506−5509. (36) Mutailipu, M.; Zhang, M.; Su, X.; Yang, Z. H.; Chen, Y. N.; Pan, S. L. Structural insights into borates with an anion-templated openframework configuration: Asymmetric K2BaB16O26 versus centrosymmetric K3CsB20O32 and Na2M2NB18O30 (M = Rb, Cs; N = Ba, Pb). Chem. - Eur. J. 2017, 23, 13910−13918. (37) Abudoureheman, M.; Han, S. J.; Wang, Y.; Liu, Q.; Yang, Z. H.; Pan, S. L. Three mixed-alkaline borates: Na2M2B20O32 (M = Rb, Cs) with two interpenetrating three-dimensional B-O networks and Li4Cs4B40O64 with fundamental building block B40O77. Inorg. Chem. 2017, 56, 13456−13463. (38) Zhang, X. Y.; Li, D. N.; Wu, H. P.; Pan, S. L.; Yang, Z. M2Ca3B16O28 (M = Rb, Cs): Structures analogous to SBBO with three-dimensional open-framework layers. RSC Adv. 2016, 6, 14205− 14210. (39) Bae, S. W.; Kim, C. Y.; Lee, D. W.; Ok, K. M. Cooperative effects of cation size and variable coordination modes of Te4+ on the frameworks of new alkali metal indium tellurites, NaIn(TeO3)2, KIn(TeO3)2, RbInTe3O8, and CsInTe3O8. Inorg. Chem. 2014, 53, 11328−11334. (40) Xia, Z. G.; Poeppelmeier, K. R. Chemistry-inspired adaptable framework structures. Acc. Chem. Res. 2017, 50, 1222−1230. (41) Kim, Y. H.; Tran, T. T.; Halasyamani, P. S.; Ok, K. M. Macroscopic polarity control with alkali metal cation size and coordination environment in a series of Tin Iodates. Inorg. Chem. Front. 2015, 2, 361−368. (42) Yu, H. W.; Zhang, W. G.; Halasyamani, P. S. Large birefringent materials, Na6Te4W6O29 and Na2TeW2O9: Synthesis, structure, crystal growth, and characterization. Cryst. Growth Des. 2016, 16, 1081−1087. (43) Lu, H. C.; Gautier, R.; Donakowski, M. D.; Tran, T. T.; Edwards, B. W.; Nino, J. C.; Halasyamani, P. S.; Liu, Z. T.; Poeppelmeier, K. R. Nonlinear active materials: An illustration of controllable phase matchability. J. Am. Chem. Soc. 2013, 135, 11942− 11950. F
DOI: 10.1021/acs.inorgchem.7b03243 Inorg. Chem. XXXX, XXX, XXX−XXX
Article
Inorganic Chemistry (44) Marvel, M. R.; Lesage, J.; Baek, J.; Halasyamani, P. S.; Stern, C. L.; Poeppelmeier, K. R. Cation−anion interactions and polar structures in the solid state. J. Am. Chem. Soc. 2007, 129, 13963− 13969. (45) 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. (46) Huang, H. W.; Tu, S. C.; Zeng, C.; Zhang, T. R.; Reshak, A. H.; Zhang, Y. H. Macroscopic polarization enhancement promoting photo- and piezoelectric-induced charge separation and molecular oxygen activation. Angew. Chem., Int. Ed. 2017, 56, 11860−11864. (47) Chang, H. Y.; Kim, S.-H.; Ok, K. M.; Halasyamani, P. S. New polar oxides: Synthesis, characterization, calculations, and structure− property relationships in RbSe2V3O12 and TlSe2V3O12. Chem. Mater. 2009, 21, 1654−1662. (48) SAINT, version 7.60A; Bruker Analytical X-ray Instruments, Inc.: Madison, WI, 2008. (49) Sheldrick, G. M. SHELXTL, version 6.14; Bruker Analytical Xray Instruments, Inc.: Madison, WI, 2008. (50) Sheldrick, G. M. SHELXTL-97: Program for Crystal Structure Refinement; University of Göttingen: Göttingen, Germany, 1997. (51) Spek, A. L. Single-crystal structure validation with the program PLATON. J. Appl. Crystallogr. 2003, 36, 7−13. (52) Kubelka, P.; Munk, F. Z. A contribution to the optics of pigments. Z. Tech. Phys. 1931, 12, 593−601. (53) Tauc, J. Absorption edge and internal electric fields in amorphous semiconductors. Mater. Res. Bull. 1970, 5, 721−729. (54) Clark, S. J.; Segall, M. D.; Pickard, C. J.; Hasnip, P. J.; Probert, M. J.; Refson, K.; Payne, M. C. First principles methods using CASTEP. Z. Kristallogr. - Cryst. Mater. 2005, 220, 567−570. (55) Jones, O. S.; Shumlak, U.; Eberhardt, D. S. An implicit scheme for nonideal magnetohydrodynamics. J. Comput. Phys. 1997, 130, 231−242. (56) Perdew, J. P.; Burke, K.; Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 1996, 77, 3865−3868. (57) Vanderbilt, D. Soft self-consistent pseudo potentials in a generalized eigenvalue formalism. Phys. Rev. 1990, 41, 7892−7895. (58) Wang, C. S.; Klein, B. M. First-principles electronic structure of Si, Ge, GaP, GaAs, ZnS, and ZnSe. I. Optical properties. Phys. Rev. 1981, 24, 3417−3429. (59) Godby, R. W.; Schlüter, M.; Sham, L. J. Self-energy operators and exchange- correlation potentials in semiconductors. Phys. Rev. 1988, 37, 10159−10175. (60) Cooper, W. F.; Larsen, F. K.; Coppens, P.; Giese, R. F., jr Electron population of accurate diffraction data. V. Structure and onecenter charge refinement of the light-atom mineral kernite, Na2B4O6(OH)2(H2O)3. Am. Mineral. 1973, 58, 21−31. (61) Dong, X. Y.; Jing, Q.; Shi, Y. J.; Yang, Z. H.; Pan, S. L.; Poeppelmeier, K. R.; Young, J.; Rondinelli, J. M. Pb2Ba3(BO3)3Cl: A material with large SHG enhancement activated by Pb-chelated BO3 groups. J. Am. Chem. Soc. 2015, 137, 9417−9422. (62) Shi, G. Q.; Wang, Y.; Zhang, F. F.; Zhang, B. B.; Yang, Z. H.; Hou, X. L.; Pan, S. L.; Poeppelmeier, K. R. Finding the next deepultraviolet nonlinear optical material: NH4B4O6F. J. Am. Chem. Soc. 2017, 139, 10645−10648. (63) 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. K3B6O10Cl: A new structureanalogous toperovskite with a large SHG response and deep UV absorption edge. J. Am. Chem. Soc. 2011, 133, 7786−7790. (64) 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. Cs3Zn6B9O21: A new member in the KBBF family without layer habits yet exhibiting the largest second harmonic generation response. J. Am. Chem. Soc. 2014, 136, 1264−1267.
(65) Burns, P. C.; Grice, J. D.; Hawthorne, F. C. Borate minerals. I. Polyhedral clusters and fundamental building blocks. Can. Mineral. 1995, 33, 1131−1151. (66) Grice, J. D.; Burns, P. C.; Hawthorne, F. C. Borate minerals. II. A hierarchy of structures based upon the borate fundamental building block. Can. Mineral. 1999, 37, 731−762. (67) Brese, N. E.; O'Keeffe, M. Bond-valence parameters for solids. Acta Crystallogr., Sect. B: Struct. Sci. 1991, 47, 192−197. (68) Zhao, S. G.; Zhang, J.; Zhang, S. Q.; Sun, Z. H.; Lin, Z. H.; Wu, Y. C.; Hong, M. C.; Luo, J. H. A new UV nonlinear optical material CsZn2B3O7:ZnO4 tetrahedra double the efficiency of second-harmonic generation. Inorg. Chem. 2014, 53, 2521−2527. (69) Blatov, V. A. Nanocluster analysis of intermetallic structures with the program package TOPOS. Struct. Chem. 2012, 23, 955−963. (70) Zhang, B. B.; Yang, Z. H.; Yang, Y.; Lee, M. H.; Pan, S. L.; Jing, Q.; Su, X. p-(p,π*) interaction mechanism revealing and accordingly designed new member in DUV/UV NLO borates LinMn‑1B2n‑1O4n‑2 (M = Cs/Rb, n = 3, 4, 6). J. Mater. Chem. C 2014, 2, 4133−4141.
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DOI: 10.1021/acs.inorgchem.7b03243 Inorg. Chem. XXXX, XXX, XXX−XXX
