Na8MB21O36 (M = Rb and Cs): Noncentrosymmetric Borates with

Apr 24, 2017 - Two noncentrosymmetric borates, Na8MB21O36 (M = Rb and Cs), have been synthesized, structurally analyzed, and characterized for the fir...
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Na8MB21O36 (M = Rb and Cs): Noncentrosymmetric Borates with Unprecedented [B21O36]9− Fundamental Building Blocks Miriding Mutailipu,†,‡ Min Zhang,*,† Xin Su,†,‡ Zhihua Yang,† and Shilie Pan*,† †

Key Laboratory of Functional Materials and Devices for Special Environments, Xinjiang Technical Institute of Physics & Chemistry, Xinjiang Key Laboratory of Electronic Information Materials and Devices, Chinese Academy of Sciences, 40-1 South Beijing Road, Urumqi 830011, China ‡ University of the Chinese Academy of Sciences, Beijing 100049, China S Supporting Information *

scientists in the field of NLO materials,10,11 birefringent materials,22 and photocatalyst fields.23 In this Communication, two noncentrosymmetric borates, Na8MB21O36 (M = Rb and Cs), were synthesized for the first time. Their structures are constructed by the same FBB [B21O36]9−, which is cotemplated by one four-connected (4c) [BO4]5− and four five-connected (5c) [B5O11]7− units. More importantly, the title compounds represent the first example of the [B21O36]9− unit as the FBB in borates. The multidirectional connections among those FBBs lead to an involuted 3D B−O framework with two types of channels, namely, 24- and 26membered-ring (MR) channels. The M atoms with large atomic radii as well as the Na atoms act as fillers and are located in the 24MR and 26-MR channels, respectively. The properties of the title compounds were tested both experimentally and theoretically. Colorless block single crystals of the title compounds were grown via spontaneous crystallization from the melt of a Na2O− Rb2O (or Cs2O)−B2O3 system. Pure samples of Na8MB21O36 (M = Rb and Cs) were prepared by a solid-state reaction with a stoichiometric mixture of Na2CO3, Rb2CO3 (or Cs2CO3), and H3BO3. The purity of as-prepared polycrystalline samples were directly confirmed by the powder X-ray diffraction (PXRD) patterns (Figure S1). Terminal stabilities of Na8MB21O36 (M = Rb and Cs) were evaluated by thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC), which show that both of them are stable up to 800 °C without any weight loss on their TGA curves, there is only one obvious endothermic peak around 727 and 780 °C for Rb- and Cs-based compounds, respectively. On the heating curves of their DSC curves (Figure S2), there are no any peaks on the cooling plots, which is caused by the high viscosity of the B-rich systems. Moreover, we melted the as-prepared samples in platinum crucibles at 820 °C and then allowed them to cool very slowly (as long as 3 weeks) to room temperature for further PXRD analyses. The PXRD patterns of the residues are identical with those of the initial samples (Figure S1), demonstrating that both of them melt congruently. Single-crystal X-ray analysis indicates that Na8RbB21O36 and Na8CsB21O36 are isostructural and crystallize in the same asymmetric space group I4̅ (No. 82) with a slight difference in the positional disorder of the Rb and Cs atoms (Table S1 and Figure S3). In brief, only the crystal structure of Na8CsB21O36 will be described in detail in the following section. The structure

ABSTRACT: Two noncentrosymmetric borates, Na8MB21O36 (M = Rb and Cs), have been synthesized, structurally analyzed, and characterized for the first time. Their fundamental building block (FBB) is determined as the unprecedented [B21O36]9− units, which is cotemplated by four-connected [BO4]5− and five-connected [B5O11]7− clusters. To the best of our knowledge, the [B21O36]9− FBB has never been reported in borates. Besides, the structure comparisons among all the available anhydrous borates with high-polymeric FBBs were carried out to enlighten the investigation of B-rich borates.

B

orates with exceptional molecular structures and physicochemical properties are extensively investigated for their potential applications in the field of laser technologies, optical communications, nonlinear-optical (NLO) materials, etc.1−4 From a synthetical point of view on the structure−property relationship, the multifunction of borates is due to the structural flexibility of the B−O units.5−8 Customarily, the B atom can be three- or four-coordinated with the O atoms to construct various oxoborate clusters, and the combination of different B−O clusters through the sharing of corners or edges will generate varied B−O fundamental building blocks (FBBs). The typical B−O FBBs include [BO3]3− in KBe2BO3F2,9 [B3O6]3− in βBaB2O4,10 [B3O7]5− in LiB3O5, CsB3O5, and CsLiB6O10,11 while with more investigations paid to the design and synthesis of borates, high-polymeric borate units such as [B5O11]7−, [B7O14]7−, [B12O24]12−, and [B18O36]18− were continuously reported.12−15 Thus far, with respect to the high-polymeric FBBs, the [B63O133]77− and [B26O42]6− B−O clusters in Cs3B7O1216 and Cs3B13O2117 are the two largest FBBs among borates, which is built by different types of B−O clusters and can be represented as 63:[(7:3Δ+4T)+10(5:3Δ+2T)+(5:2Δ+3T)+T] and 26:[2(5:4Δ+T)+4(3:2Δ+T)+4Δ] based on the scheme proposed by Christ and Clark.18 Until now, the B-rich system with a large boron proportion is propitious to eliminating the terminal O atom of the B−O units and expected to exhibit better transmission in an ultraviolet (UV) or deep-UV region19−21 and then improves the laser-damage thresholds. Therefore, the B-rich system combined with alkali and alkaline-earth metals (without d−d or f−f electron transitions) becomes a new hot spot for chemists and materials © 2017 American Chemical Society

Received: March 14, 2017 Published: April 24, 2017 5506

DOI: 10.1021/acs.inorgchem.7b00671 Inorg. Chem. 2017, 56, 5506−5509

Communication

Inorganic Chemistry of Na8CsB21O36 features an involuted 3D anionic framework composed of the [B21O36]9− FBB with two different 2D channels, which are filled with the Cs and Na atoms (Figure 1a). The

Figure 2. Topological models of Na8CsB21O36.

Table 1. Anhydrous Borates with High-Polymeric FBBs Figure 1. (a) Crystal structure viewed in the (001) plane. (b) FBB of Na8CsB21O36. (c) Type A channel in the direction of the c axis. (d) Diameter of the type A channel.

asymmetric unit of Na8CsB21O36 consists of two Na atoms, one Cs atom, six B atoms, and nine O atoms (Table S3). Among them, the B(1,2,3) atoms are three-coordinated to the [BO3]3− triangles, while the B(4,5,6) atoms are four-coordinated to the [BO4]5− tetrahedra, with the B−O distances [1.335(4)− 1.493(4) Å] and O−B−O angles [104.5(2)−125.6(3)°] in the typical ranges of those reported borates.24−27 Two [B(4,5)O4]5− and three [B(1,2,3)O3]3− units join together to form a [B5O11]7− cluster, and then centered [B(6)O4]5− is surround by four [B5O11]7− clusters to build a [B21O36]9− high-polymeric group, which is the minimum repeating unit and the FBB of Na8CsB21O36 with the formula of 21:[4(5:3Δ+2T)+T] (Figure 1b). As far as we know, the borates with the [B21O36]9− FBB have never been reported, and here we give the first example in this work. Then the terminal O atoms of the [B21O36]9− FBB act as linkers to yield of the 3D B−O anionic framework (Figure 1a) with two types of channels, type A channels with 24-MRs (Figure 1c,d) and type B channels with 26-MRs running along the c axis (Figure S4). Then the Cs atoms with the largest atomic radii are located in the type A channels, while the Na atoms fill in the type B channels. The bond-valence calculation for Cs(1) is about 0.476 (coordination number = 12; Cs−O bond length = 3.501− 3.819 Å) and less than the ideal value, which is caused by the location of the Cs atoms in the big channels, while the Rb atoms (coordination number = 11; Rb−O bond length = 3.152−3.953 Å) in Na8RbB21O36 are also filled in the near-size (diameter ≈ 6.2 Å) channel, and the ionic radius of Rb+ is smaller than that of Cs+, so Rb+ is small enough to hold the channels, leading to the positional disorder of Rb atoms in the structure of Na8RbB21O36 (Figure S3), which is similar to the disordered [B(OH)4] units in the structure of LiBa3(OH)[B9O16][B(OH)4].28 The involuted 3D network of Na8CsB21O36 can be simplified by considering the [B(6)O4]5− and [B5O11]7− units as 4c and 5c nodes, respectively. As a result, Na8CsB21O36 can be reduced to a topological 4,5-c (Figure 2a) net with the Schläfli symbol29 of {45.63.72}{4(66)}, which shows a new type of topology according to the TOPOS database (Figure 2b).30 Stimulated by the unprecedented [B 21O36]9− FBB in Na8MB21O36(M = Rb and Cs), all of the anhydrous borates with high-polymeric FBBs (number of B atoms NB > 10) were summarized in Tables 1 and S6 after thousands of anhydrous borates were checked based on a survey of the Inorganic Crystal Structure Database (ICSD-3.5.0, the latest release of ICSD2016/11/02). The special crystal chemistry of borates with high-

formula

FBB

Li3KB4O814 Li6Rb5B11O2237 LiNa2Sr8B12O24F6Cl14 Li3NaBaB6O1231 Pb6(B10O21)38 Sr8M(B18O36)15,32 NaSr7Al(B18O36)33 Rb3B7O1234 Cs3B7O1216 Cs3B13O2117 Pb4Zn2B10O2139 Na6B13O22.540 M5B19O31 (M = K and Rb)36,41 Ba2B10O1742 δ-CsB5O835 Ag2CsB15O2443 Sr2B16O2644

12:[6Δ+6T] 11:[2(5:3Δ+2T)+Δ] 12:[6Δ+6T] 12:[6Δ+6T] 10:[2(4:2Δ+2T)+ 2Δ] 18:[6(3:2Δ+T)] 18:[6(3:2Δ+T)] 14:[2(5:3Δ+2T)+(3:2Δ+T)+T] 63:[(7:3Δ+4T)+10(5:3Δ+2T)+(5:2Δ+3T)+T] 26:[2(5:4Δ+T)+4(3:2Δ+T)+4Δ] 10:[2(3:Δ+2T)+2Δ+2T)] 13:[(5:3Δ+2T)+2(4:2Δ+2T)] 19:[2(5:4Δ+T)+2(3:2Δ+T)+2(Δ)+(T)] 10:[2(3:Δ+2T)+4(Δ)] 10:[2(5:4Δ+T)] 15:[2(5:4Δ+T)+2.5:2Δ+0.5T)] 16:[(5:4Δ+T)+3(3:2Δ+T)+2Δ]

polymeric FBBs (NB > 10) can be concluded by the following main features: (1) With a decrease of the ratio of A (cation)/B, the dimensions of the total B−O framework increase from an isolated (0D), 2D-layered configuration to a 3D B−O configuration. With respect to the isolated B−O configuration, the circular B−O FBBs take up a majority (7/9) of them, such as [B12O24]12− (12-MRs) in Li3KB4O8,14 LiNa2Sr8B12O24F6Cl14, and Li3NaBaB6O1231 and [B18O36]18− (12-MRs) in Sr8M(B18O36) (M = Mg, Zn, and Cd)15,32 and NaSr7Al(B18O36),33 while for those borates containing a 2D-layered B−O configuration, the [B63O133]77−, [B26O42]6−, and [B14O24]6− FBBs in related compounds are cotemplated by three different types of B−O clusters, namely, [B7O16]11‑, [B5O11]7−, and [BO3]3− units for Cs3B7O12,16 [B5O10]5−, [B3O7]5−, and [BO3]3− groups for Cs3B13O21,17 and [B5O11]7−, [B3O7]5−, and [BO3]3− clusters for Rb3B7O12.34 The Cs+ and Rb+ ions locate in or around those 2D layers to construct the final 3D structures. (2) The studies in their metal cation sections show that almost all of the borates with high-polymeric FBBs contain cations with large ionic radii, such as the Cs+ ion in Cs3B13O21,17 δ-CsB5O8,35 Cs3B7O12,16 and Na8CsB21O36 and the Rb+ ion in Rb3B7O12,34 Rb5B19O31,36 and Li6Rb5B11O22,37 as well as other metal ions with large ionic radii in related compounds. Interestingly, the large size atoms always tend to make the whole construction with channels or layers more stable and closer. Considering the noncentrosymmetric structure attributes, second-harmonic-generation (SHG) measurements were performed on the polycrystalline samples of Na8MB21O36 (M = Rb 5507

DOI: 10.1021/acs.inorgchem.7b00671 Inorg. Chem. 2017, 56, 5506−5509

Communication

Inorganic Chemistry and Cs) using the Kurtz−Perry method,45 and 1064 nm light was generated with Q-switched Nd:YVO4 at room temperature. The SHG intensities for Rb- and Cs-based compounds were only about 1/10 that of KH2PO4. According to anionic group theory, the [BO4]5− units without large structural distortion contribute less to the SHG response, which is similar to the rigid SiO4 groups,46 while the main contributor [BO3]3− groups in the title compounds are adopted into opposite orientations, which will weaken the SHG responses. The UV−vis−near-IR (NIR) diffuse-reflectance spectra, plotted in Figure S5, reveal that their UV cutoff edges are below 200 nm. We performed first-principles calculations in the CASTEP package only based on Na8CsB21O36 without a disordered structure. The results show that Na8CsB21O36 has a direct band gap of 4.67 eV (Figure S6) because the valence-band (VB) maximum and the conduction-band (CB) minimum are both located at the same Γ point. Because the optical properties are mainly determined by the electronic transition among the states near the Fermi level, the electronic states at the top of the VB and the bottom of the CB were analyzed. As presented in Figure 3a,

Experimental details, crystal data, XRD patterns, TGA− DSC curves, crystal structures, UV−vis−NIR spectra, and electronic band structure (PDF) Accession Codes

CCDC 1536852−1536853 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 [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: [email protected] (M.Z.). *E-mail: [email protected] (S.P.). ORCID

Zhihua Yang: 0000-0001-9214-3612 Shilie Pan: 0000-0003-4521-4507 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was financially supported by the National Natural Science Foundation of China (Grants 21501194, 51425206, 91622107, and 11474353), National Key Research Project (Grants 2016YFB1102302 and 2016YFB0402104), Xinjiang Key Research and Development Program (Grant 2016B02021), Major Program of Xinjiang Uygur Autonomous Region of China during the 13th Five-Year Plan Period (Grant 2016A02003), National Key Research Projects (Grant SQ2016YFGX070132), and Science and Technology Project of Urumqi (Grant P161010003).

Figure 3. (a) Density of states and partial density of states of Na8CsB21O36. (b) Calculated refractive indices n and birefringence Δn curves of Na8CsB21O36.

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the regions between −21.5 and −16.5 eV mainly consist of 2p orbitals of the Na atoms, 2s orbitals of the O atoms, and a fraction of 2p orbitals of the O atoms, and the region from −9 eV to the Fermi level is mostly from contributions of O and B 2p orbitals with a small amount of Cs 5p orbitals. The top of the VB is mainly composed of 2p orbitals of the O atoms. The bottom of the CB is mainly made up by 2p orbitals of the B and O atoms and Cs 5p and Na 3s orbitals (Figure 3a). Accordingly, the absorption spectrum can be assigned as the electronic transition from the O 2p states to the B 2p states. The simulated refractive indices no, ne, and birefringence Δn curves of Na8CsB21O36 are shown in Figure 3b. It is clear that Na8CsB21O36 is a positive uniaxial crystal and the birefringences of Na8CsB21O36 are about 0.0361@1064 and 0.0386@532 nm. In conclusion, two isostructural mixed-alkali-metal borates Na8RbB21O36 and Na8CsB21O36 have been synthesized. The unprecedented [B21O36]9− FBB was found and can be represented as 21:[4(5:3Δ+2T)+T], which is constructed by one 4c [B(6)O4]5− and four 5c [B5O11]7− clusters. Both compounds exhibit congruent melting behavior, SHG effects, and UV cutoff edges.

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S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.7b00671. 5508

DOI: 10.1021/acs.inorgchem.7b00671 Inorg. Chem. 2017, 56, 5506−5509

Communication

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DOI: 10.1021/acs.inorgchem.7b00671 Inorg. Chem. 2017, 56, 5506−5509