NaCa5BO3(SiO4)2 with Interesting Isolated [BO3] and [SiO4] Units in

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NaCa5BO3(SiO4)2 with Interesting Isolated [BO3] and [SiO4] Units in Alkali- and Alkaline-Earth-Metal Borosilicates Zhaohong Miao,†,‡,§ Yun Yang,†,§ Zhonglei Wei,†,‡ Zhihua Yang,† Sujuan Yu,† and Shilie Pan*,† †

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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, People’s Republic of China ‡ Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, People’s Republic of China S Supporting Information *

ABSTRACT: A new borosilicate, NaCa5BO3(SiO4)2, has been synthesized by a high-temperature solution method, which crystallizes in the centrosymmetric monoclinic space group P21/c (No. 14), having a tangled three-dimensional (3D) network including isolated [BO3] triangles, isolated [SiO4] tetrahedra, and [CaOn] (n = 7−9) and [NaO7] polyhedra. According to our surveys, it is the first compound containing both isolated [BO3] triangles and isolated [SiO4] tetrahedra in alkali- and alkaline-earth-metal borosilicates, which enriches the structure chemistry of borosilicates. The UV−vis−NIR diffuse reflectance spectrum shows that NaCa5BO3(SiO4)2 exhibits a wide transparent region which covers the near-IR, visible, and UV windows and displays a short UV cutoff edge at about 240 nm. Additionally, the thermal behavior (TG and DSC) and IR spectrum were also analyzed. For a deeper understanding of the relationships between the structure and properties, an analysis of theoretical calculations by density functional theory was also performed.

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INTRODUCTION The crystal chemistry of borates has attracted a huge amount of interest owing to their broad applications such as birefringent and nonlinear optical (NLO) materials, electrode materials, phosphors materials, and laser materials.1−5 It is widely acknowledged that the connection of B and O atoms can easily form [BO3] triangles or [BO4] tetrahedra. Furthermore, by vertex or edge sharing, this connection facilitates the formation of multiple B−O structures covering zero-dimensional (0D) clusters to 3D frameworks.6−14 For example, in α- and β-BaB2O4 (BBO), there are isolated [B3O6] rings,15 and in LiB3O 5 (LBO), there is a 3D B−O framework.16 These B−O units are conducive in broadening the transparent range of the UV or deep-UV region, causing a considerable second-harmonic generation (SHG) response, and generating a befitting birefringence.17−23 Meanwhile, as natural minerals, silica and silicates are the largest components of the earth’s crust and mantle by far.24−26 The raw materials of silica and silicates are equally important for mass production. On this account, they have been one of the most important subjects of scientific research by applied scientists and geoscientists in the cement, ceramic, glass, and other industries.27,28 In addition, intensive fundamental research on silicates has been explored over the years. Owing to their enormous variability, silicates are ideal materials for the study of crystallographic principles and general chemistry.29−31 More recently, the combination of two different anionic groups in one compound, such as borogermanates (Sr3Ge2B6O16, © XXXX American Chemical Society

band gap 5.83 eV), borophosphates (K7B2P5O19, cutoff edge 190 nm), and borosilicates (Cs2B4SiO9, 4.6 KDP and cutoff edge 190 nm), has been proved to be an valid way to generate moderate birefringence, obtain large SHG responses, shorten the cutoff edge, etc.24,32−39 Especially, much attention has been paid to borosilicates due to their excellent performance.40−44 On account of the various coordinations of both B−O and Si− O units, the combination of two units can contribute to a diversity of structures, such as one-dimensional (1D) chains [BSiO 5 ] in CeBSiO 5 , 45 two-dimensional (2D) layers [Si3B6O27] in BaY6(Si3B6O24)F2,46 three-dimensional (3D) frameworks B(SiO4)4 in Li4B4Si8O24,47 etc. Further, based on the basis of a survey of anhydrous and disorder-free alkaliand/or alkaline-earth-metal borosilicates in the Inorganic Crystal Structure Database (ICSD), only 16 compounds have been synthesized. Considering the dimensionality of anion groups in these compounds, we find that the 2D layers and 3D frameworks of anionic structures have been reported already. However, 0D clusters or oligomers and 1D chains have never been observed. Enlightened by the ample results gained from above strategies, via use of different molar ratios of the ingredients, we have synthesized a new alkali- and alkaline-earth-metal cations containing borosilicate, NaCa5BO3(SiO4)2, which is the first compound containing both isolated [BO3] and Received: January 1, 2019

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DOI: 10.1021/acs.inorgchem.9b00002 Inorg. Chem. XXXX, XXX, XXX−XXX

Article

Inorganic Chemistry isolated [SiO4] groups in alkali- and/or alkaline-earth-metal borosilicates. Herein, the synthesis, crystal structure, thermal behaviors, and spectrum properties are reported. The relationship between crystal structure and optical properties is explored by first-principles calculations. In addition, the structures of the 16 borosilicates mentioned above are also discussed in this paper.

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Table 1. Crystal Data and Structure Refinement Details for NaCa5BO3(SiO4)2 empirical formula formula wt temp (K) wavelength (Å) cryst syst, space group a (Å) b (Å) c (Å) β (deg) V (Å3) Z, calcd density (Mg/m3) abs coeff (mm−1) F(000) θ range for data collection (deg) limiting indices

EXPERIMENTAL SECTION

Reagents. Na2CO3 (Shanghai Aladdin Reagent Co., Ltd., 99.0%), CaCO3 (Tianjin Bodi Chemical Co., Ltd., 99.0%), SiO2 (Shanghai Aladdin Reagent Co., Ltd., 99.0%), NaF (Tianjin Bodi Chemical Reagent Co., Ltd., 99.0%), CaF2 (Tianjin Bodi Chemical Reagent Co., Ltd., 99.0%), and B2O3 (Shanghai Aladdin Reagent Co., Ltd., 98.0%) were selected to obtain the target product. Crystal Synthesis. Single crystals of NaCa5BO3(SiO4)2 were obtained by a high-temperature solution method using CaF2−B2O3− NaF as the flux system. Mixtures of Na2CO3, CaCO3, B2O3, SiO2, NaF, and CaF2 in a molar ratio of 2:7:3:2:10:2 were prepared in a platinum (Pt) crucible, which was put into a programmabletemperature furnace. In order to ensure the mixtures melted completely, they were heated to 870 °C and maintained for 10 h at that temperature. Then the solution was quickly cooled to 820 °C and further cooled to 600 °C at a rate of 2 °C h−1. Finally, it was cooled to 25 °C at a speed of 30 °C h−1. Transparent and colorless NaCa5BO3(SiO4)2 crystals were obtained. Solid-State Synthesis. The NaCa5BO3(SiO4)2 polycrystalline materials were obtained by solid-state reaction technique. Mixtures of Na2CO3 (0.1985 g, 1.88 mmol), CaCO3 (1.7803 g, 17.79 mmol), B2O3 (0.1304 g, 1.87 mmol), and SiO2 (0.4500 g, 7.49 mmol) were ground thoroughly and put into a Pt crucible. The samples were heated to 890 °C and then maintained at that temperature for 100 h and ground intermittently. Powder X-ray diffraction (PXRD) indicates that a pure NaCa5BO3(SiO4)2 powder sample was obtained (Figure 1).

no. of collected/unique rflns completeness to θ = 27.661 (%) refinement method no. of data/restraints/params goodness of fit on F2 final R indices (I > 2σ(I))a R indices (all data)a extinction coeff largest diff peak and hole (e Å−3)

NaCa5BO3(SiO4)2 466.38 296(2) 0.71073 monoclinic, P21/c 14.144(3) 6.826(19) 10.504(4) 100.337(4) 998(3) 4, 3.105 3.027 928 2.928−27.661 −18 ≤ h ≤ 18 −8 ≤ k ≤ 8 −12 ≤ l ≤ 13 2306/2306 (Rint = 0.076) 99.90 full-matrix least squares on F2 2306/0/182 1.029 R1 = 0.0671, wR2 = 0.1413 R1 = 0.0905, wR2 = 0.1530 0.0011(5) 1.229 and −1.193

R1 = ∑||Fo| − |Fc||/∑|Fo| and wR2 = [∑w(Fo2 − Fc2)2/∑wFo4]1/2 for Fo2 > 2σ(Fo2). a

displacement parameters are given in Table S1 in the Supporting Information. Interatomic bond lengths and angles are given in Table S2 in the Supporting Information. Powder X-ray Diffraction. PXRD patterns were taken on an automated Bruker D2 X-ray diffractometer at room temperature that was equipped with a diffracted beam monochromator set for Cu Kα radiation (λ = 1.5418 Å), with scanning over the range 2θ = 10−70°. The step width of 2θ was 0.01°, and the fixed counting time was 0.5 s/step. The PXRD pattern for the pure powder sample of NaCa5BO3(SiO4)2 is shown in Figure 1. According to the singlecrystal modes, the calculated data and experimental data are in perfect agreement, which indicates that the structural model is reasonable. IR Spectrum. The infrared spectrum was obtained on a Shimadzu IR Affinity-1 Fourier transform infrared spectrometer in the wavelength range from 400 to 4000 cm−1. The test was carried out by thoroughly mixing the sample and dried KBr (5 mg of the sample and 500 mg of KBr). UV−vis−NIR Diffuse Reflectance Spectroscopy. The UV− vis−NIR diffuse reflectance spectrum of NaCa5BO3(SiO4)2 powder sample was recorded on a SolidSpec-3700DUV spectrophotometer at room temperature utilizing tetrafluoroethylene as the standard with scanning wavelength over the range of 190−2600 nm. The absorption data were obtained by the Kubelka−Munk function: F(R) = (1 − R)2/2R = K/S, where R is the reflectance, K is the absorption, and S is the scattering.50 Thermal Analysis. Thermogravimetry and differential scanning calorimetry (TG-DSC) for NaCa5BO3(SiO4)2 was carried out on a NETZSCH STA 449 F3 simultaneous thermal analyzer. A pure sample of the title compound was put into a Pt crucible and heated over the range of 40−1240 °C with a speed of 5 °C min−1 under flowing nitrogen. Theoretical Calculations. Density functional theory (DFT), electronic structure, and optical property calculations were implemented in the CASTEP package.51 For embodying correlation, core−electron interactions were characterized by norm-conserving

Figure 1. Powder XRD patterns of NaCa5BO3(SiO4)2. Single-Crystal X-ray Diffraction. The crystal of NaCa5BO3(SiO4)2, which features colorless and transparent block shape with dimensions 0.134 × 0.09 × 0.07 mm3, was filtered to determine the structure. The structure was observed by single-crystal X-ray diffraction on an APEX II CCD diffractometer using monochromated Mo Kα radiation (λ = 0.71073 Å) at 296(2) K and integrated with the SAINT program.48 The direct methods of SHELXS-97 were adopted to handle the structure.48 Aiming to refine all atoms, we used full matrix least-squares techniques; the final leastsquares refinement was on Fo2 with data having Fo2 ≥ 2σ(Fo2). The structure was checked for missing symmetry elements with the program PLATON,49 and there were no higher symmetries. Relevant crystallographic data and structure refinement information are displayed in Table 1. Atomic coordinates and equivalent isotropic B

DOI: 10.1021/acs.inorgchem.9b00002 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry

Figure 2. (a) Arrangement of [BO3] triangles and [SiO4] tetrahedra. (b) 1D ∞[NaBSi2O11] chains. (c) 1D ∞[Ca(2)O4] chains. (d) 2D ∞[Ca(3)O6] layer. (e) 2D ∞[Ca(5)O7] layer. (f) 3D framework of the Ca−O structure. (g) 3D framework of NaCa5BO3(SiO4)2. pseudopotentials (NCP).52 Meanwhile the generalized gradient approximation (GGA) of Perdew−Buker−Ernzerhof (PBE) was exerted. Then geometry optimization of NaCa5BO3(SiO4)2 in the unit cell was performed with a good converged criterion which was fixed to the origin structure. The valence states are as follows: Na 3s1, Ca 4s2, B 2s22p1, Si 3s23p2, and O 2s22p2. The value of the plane-wave basis cutoff energy was 800 eV, and 2 × 5 × 3 Monkhorst−Pack kpoint meshes were used in the calculations.

Ca−O structures interconnect with each other to build a 3D Ca−O framework (Figure 2f). Finally, the 3D Ca−O framework connects with ∞[NaBSi2O11] chains, forming the whole 3D NaCa5BO3(SiO4)2 structure (Figure 2g). The bond valence sums of each atom in NaCa5BO3(SiO4)2 were calculated and are given in Table S1. The valence sums are consistent with normal oxidation states. Crystal Structure Comparison. Aiming to further explore the crystal structure diversities of B−O and Si−O units, we chose the available anhydrous and disorder-free alkali- and/or alkaline-earth-metal cation containing borosilicates according to the ICSD. The research shows that there are 16 compounds, in addition to the title compound, which meet the above conditions. They are given in Table S3. The anionic groups of these compounds display abundant structural diversity. For the B−O groups, they all belong to 0D structures, which are [BO4] tetrahedra, [B2O7] dimers, and [B3O6], [B4O9], [B4O10], and [B4O12] clusters (Figure S1). Nevertheless, as shown in Figure S2, the Si−O structures display luxuriant diversity. (1) For the title compound NaCa5BO3(SiO4)2, LiBSiO4,53 NaBSiO4,54,55 Ca2B2SiO7,56 Cs2B4SiO939,57 and CsB3SiO7,36 they all contain isolated [SiO4] tetrahedra. Only in NaCa5BO3(SiO4)2, it includes isolated [BO3] simultaneously. It is rare that isolated [BO3] groups appear in borosilicate. In LiBSiO4 and NaBSiO4, the B−O units are isolated [BO4] tetrahedra. In Ca2B2SiO7, Cs2B4SiO9, and CsB3SiO7, the B−O groups are [B2O7] dimers, [B3O6] rings, and [B4O9] clusters, respectively. The [B2O7] dimers are formed by two corner-sharing [BO4] groups. The [B3O6] rings are built by three corner-sharing [BO3] triangles, and the [B4O9] clusters are formed by two [BO3] and [BO4] groups which are conjoined alternatively. (2) In SrB2Si2O8,58 Ba(B2Si2O8),59 and CaB2Si2O8,60 the anionic groups comprise isolated [Si2O7] and [B2O7] dimers which are formed by two [SiO4] and [BO4] groups via corner sharing, respectively. (3) In CsBSi2O661,62 and Ba2Ca(BSi2O7)2,27,63 isolated [Si4O12] rings are formed by four corner-sharing [SiO4] tetrahedra. However, the B−O groups are different. The former contains isolated [BO4] tetrahedra, and the latter comprises [B4O12] rings built by four corner-sharing [BO4] tetrahedra. (4) There

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RESULTS AND DISCUSSION Crystal Structure of NaCa 5 BO 3 (SiO 4 ) 2 . NaCa5BO3(SiO4)2 crystallizes in monoclinic space group P21/c (No. 14). The asymmetric unit features five independent Ca atoms, one independent Na atom, one independent B atom, 2 independent Si atoms, and 11 independent O atoms (Table S1 in the Supporting Information). In the structure, the Si atoms show one form of coordination, isolated [SiO4] tetrahedra (Figure 2a), and the lengths of Si−O bonds range from 1.613(7) to 1.658(7) Å, with the O−Si−O angles ranging from 105.7(4) to 113.8(4)°. The B atoms connect with O atoms, building isolated [BO3] triangles (Figure 2a), while the distances between B and O atoms range from 1.363(11) to 1.398(11) Å, with the angles in the range of 118.2(7)− 121.6(8)°. The Na+ cations coordinate with seven O atoms building isolated [NaO7] polyhedra, and the Na−O bond lengths are over the range of 2.361(7)−2.971(7) Å. The [BO3] and [SiO4] units further connect with the [NaO7] polyhedra by edge- or vertex-sharing O atoms to build 1D ∞[NaBSi2O11] chains, as shown in Figure 2b. The Ca2+ cations are joint with O atoms, forming [CaOn] (n = 7−9) polyhedra, and the lengths of Ca−O bonds are over the range of 2.289(7)− 2.945(6) Å. However, Ca(1) and Ca(4) coordinate with O atoms, forming isolated [CaO7] polyhedra. Ca(2) coordinates with eight O atoms to give [CaO8] polyhedra, which further polymerize to form 1D ∞[Ca(2)O4] chains by face sharing along the a axis as shown in Figure 2c. In addition, Ca(3) and Ca(5) are bonded to eight and nine O atoms to build [CaO8] and [CaO9] polyhedra, and they further develop 2D ∞[Ca(3)O6] and ∞[Ca(5)O7] layers by vertex sharing and edge sharing (Figures 2d,e), respectively. Furthermore, the different C

DOI: 10.1021/acs.inorgchem.9b00002 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry

covering from near-IR to the UV windows. As shown in Figure 4, the cutoff edge of NaCa5BO3(SiO4)2 is 240 nm.

are [Si2O6] chains, [Si4O12] chains, and [Si6O16] chains in Li4B4Si8O24,47 KBSi2O6,24,62,64 and NaBSi3O8;65,66 they all contain isolated [BO4] groups as in KNa2B3Si12O30.67 Differently, KNa2B3Si12O30 contains isolated [Si12O30] clusters which are constructed by 12 [SiO4] tetrahedra. For the B−Si−O structures, except for the title compound NaCa5BO3(SiO4)2, the B−O and Si−O groups in the other 16 compounds are all connected with each other to form a 2D layer or 3D framework. According to our research, in the alkaliand/or alkaline-earth-metal cation containing borosilicates, NaCa5BO3(SiO4)2 is the first case which has isolated [BO3] and isolated [SiO4] anionic groups concurrently. Thermal Analysis. The TG-DSC curves of a pure sample of NaCa 5 BO 3 (SiO 4 ) 2 are shown in Figure S3. NaCa5BO3(SiO4)2 demonstrates no obvious weight loss and decomposition up to 1240 °C. There is no endothermic peak that can be observed from room temperature to 1240 °C from the DSC curve. For the sake of verifying the thermal property of NaCa 5 BO 3 (SiO 4 ) 2 , a pure solid sample of NaCa5BO3(SiO4)2 was placed into a Pt crucible with heating to 1240 °C and maintained at this temperature for 24 h; then it was slowly cooled to 25 °C. In the above process, the sample did not melt, and PXRD data of the residue reveals that it is stable below 1240 °C (Figure 1). Because of its stability at high temperature, it requires the flux method when we created large crystals. Experimental Optical Properties. IR spectroscopic measurement was applied in verifying the coordination environment about the B and Si atoms in the title compound. The IR spectrum and the assignment of the absorption peaks are shown in Figure 3. The main IR absorption peaks at 1195,

Figure 4. UV−vis−NIR diffuse reflectance spectrum of NaCa5BO3(SiO4)2.

Electronic Structure and Calculated Optical Properties. The calculated band structure and partial density of states (PDOS) of NaCa5BO3(SiO4)2 are shown in Figures S4 and S5. A direct band gap of 4.512 eV is along highly symmetric G points with a dense band distribution. It can be seen that O 2p states occupy the top of occupied state bands, while at the bottom of unoccupied states above EF (Fermi level), Na s/p and Ca 3d states are the main constituents. The band gap Eg is found to be determined by Na s in the conduction bands and O p in the valence bands. NaCa5BO3(SiO4)2 belongs to the monoclinic P21/c space group. As shown in Figure S6 in the Supporting Information, NaCa5BO3(SiO4)2 is an optically negative biaxial crystal (n3 − n2) < (n2 − n1) with a relatively small birefringence of 0.0243@ 1024 nm. According to the REDA (response electron distribution anisotropy) method, which has been successfully applied to UV and IR crystals,76−78 the birefringence is mainly affected by the electron distribution response of covalent groups. In this method, each group is assigned a REDA value (VREDA) to characterize thir optical anisotropy. A large REDA value means a large optical anisotropy. The bond population analysis is shown in Table S4; a relatively high value (>0.2) means that the bond covalency is taken into account and, consequently, the [BO3] planar groups and the [SiO4] tetrahedra play an important role in birefringence of NaCa5BO3(SiO4)2. The arrangements of molecules and their microscale structures have an important influence on the anisotropy of birefringence; the effect of the [BO3] groups to the optical anisotropy has been analyzed in detail in a previous article.79 As shown in Figure S7, the relative positions of [BO3] and [SiO4] in the polarized direction are displayed (a [0.0709928, 0, 0.005516], b [0, −0.1453519, 0], c [0.0091377, 0, 0.0962079]; these three directions were obtained by analyzing the optical matrix). The [BO3] groups with a parallel arrangement are well-spaced in the 3D pores which are formed by the [SiO4] tetrahedra and the CaOn (n = 7−9) polyhedra and have relatively stronger optical anisotropy (VREDA = 0.0057). In addition, weak optical anisotropy in [SiO4] and the configuration are strewn at random; herein, the [SiO4] (VREDA = 0.0025) groups have a relatively small contribution (∼30%) to the birefringence of NaCa5BO3(SiO4)2.

Figure 3. IR spectrum for NaCa5BO3(SiO4)2.

1292, 1329, and 843−952 cm−1 could be due to the asymmetric and symmetric stretching vibrations of [BO3]. Then the peak at 733 cm−1 is due to the out-of-plane bending of [BO3]. The band at 618 cm−1 belongs to the in-plane bending of [BO3]. In addition, the absorption peak at 593 cm−1 is caused by the bending of [BO3]. The three peaks located at 770, 794, and 1007 cm−1 can be assigned to the symmetric stretching vibrations of [SiO4]. The band at 508 cm−1 may be the rocking vibration of [SiO4]. The assignments are in good agreement with those reported previously.13,21,68−75 The UV−vis−NIR diffuse reflectance spectrum of NaCa5BO3(SiO4)2 also shows a transparent region D

DOI: 10.1021/acs.inorgchem.9b00002 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry

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CONCLUSION A new complex alkali- and alkaline-earth-metal borosilicate, NaCa5BO3(SiO4)2, was obtained by a high-temperature solution method. It shows a unique structure type in comparison with other borosilicates. The anionic groups have a 0D structure in NaCa5BO3(SiO4)2. To the best of our knowledge, it is the first example of alkali- and alkalineearth-metal borosilicates that contains both isolated [BO3] triangles and isolated [SiO4] tetrahedra, which enriches the structure chemistry of borosilicates. The IR spectrum and the BVS calculations further demonstrate the validity of the structure. A diffuse reflection spectrum indicates that it has a UV cutoff edge at 240 nm. Thermal behavior analysis and a melt experiment confirm that it remains stable until 1240 °C. These strategies and insights should motivate other researchers to explore and synthesize novel inorganic functional crystals with multiple structures and intriguing properties.

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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.9b00002. Crystallographic data, structure comparison data, TGDSC curves of the compound, and DFT calculation results DOCX) Accession Codes

CCDC 1868173 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 Author

*E-mail for S.P.: [email protected]. ORCID

Shilie Pan: 0000-0003-4521-4507 Author Contributions §

Z.M. and Y.Y. contributed equally to this work.

Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by the Xinjiang International Science & Technology Cooperation Program (Grant No. 2017E01014), Tianshan Innovation Team Program (Grant No 2018D14001), the National Natural Science Foundation of China (Grant Nos. U1703132, 51872325, 51425206), and the Science and Technology Project of Urumqi (Grant Nos. P161010002, G161020001).

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