Communication pubs.acs.org/IC
An Ultraviolet Nonlinear Optic Borate with 13-Ring Channels Constructed from Different Building Units Er-Rong Wang,† Jian-Hao Huang,† Su-Juan Yu,† You-Zhao Lan,† Jian-Wen Cheng,*,† and Guo-Yu Yang*,‡ †
College of Chemistry and Life Sciences, Zhejiang Normal University, Jinhua, Zhejiang 321004, China MOE Key Laboratory of Cluster Science, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081, China
‡
S Supporting Information *
LiBa3(OH)[B9O16][B(OH)4] shows gigantic 21R channels built by a corner-sharing B9O19 cluster and larger SHG intensities (about 3.1 × KDP).18 To date, borate frameworks usually contain only one kind of B−O unit; the presence of two types of B−O units is rare.20,21 If two distinct types of B−O clusters incorporate into the same structure, new types of borate with extended functions would be expected. Up to now, only several open framework borates contain more than one type of cluster.22,23 For example, Rowsell et al. reported a novel crystalline open-framework cobalt borate containing B3O7 and B4O9 clusters, which has shown good ion-exchange properties;22 Wang et al. obtained a new boron oxide with 13R and 14R channels containing B3O7 and B5O11 clusters; this compound acts as a good host for Eu3+doped optical materials and is a good white-light emitting material.23 As a continuation of our search for borates with NLO properties,17,18,24 we report a chiral open-framework boron oxide Na2B9O15(H2O)(H3O) (1), which contains 13R large channels by combining B3O7 and B6O13 clusters; compound 1 shows a moderate SHG signal intensity comparable to that of KDP. Compound 1 was synthesized by the solvothermal reactions of H3BO3, NaBO2·4H2O, and 1,3-diaminopropane at 170 °C for 7 days. The powder X-ray diffraction patterns indicate the phase purity of 1 (Figure S1).25 The infrared spectrum confirms the existence of BO3 and BO4. The peaks of BO4 are around 1002 and 967 cm−1, while the peak at 1345 cm−1 is assigned as the asymmetric stretch of BO3 (Figure S2). It should be stressed that 1 could not be obtained if any other amine source was used instead of 1,3-diaminopropane. Compound 1 exhibits a monoclinic space group P21 via single crystal X-ray analysis (Table S1).26 The B−O anionic framework is built by the B3O7 and B6O13 clusters with pure B−O−B bonds. Each B3O7 cluster consists of one BO4 tetrahedron and two BO3 triangles and form a three-ring structure, while each B6O13 cluster consists of three three-rings with three BO4 tetrahedrons and three BO3 triangles (Figure 1a). Each B3O7 cluster is linked to the two nearest B3O7 and two B6O13 clusters, and each B6O13 unit is linked to two B3O7 clusters and four nearest neighbors. The 3D chiral openframework finally formed through such a connection between
ABSTRACT: Under solvothermal conditions, a chair open-framework borate, Na2B9O15(H2O)(H3O) (1), has been synthesized. Compound 1 shows regular pores of zeolites as well as nonlinear optical (NLO) properties of borates. The large 13-ring channels of the boron oxide framework are constructed from different cluster units of B3O7 and B6O13 with three-ring units. The second harmonic generation (SHG) signal intensity of 1 is similar to that of KH2PO4 (KDP) and gradually increased with larger particle size. Compound 1 is a potential UV NLO material for its short wavelength absorption edge.
Z
eolites are of great interest owing to their important applications in host−guest assemblies, gas adsorption/ separation, and catalysis.1−3 The structures of zeolites show an intriguing variety of topologies formed by corner-sharing TO4 tetrahedra (T = Si, P, Al, etc.).4,5 It is known that the introduction of cluster building units is an effective synthetic route to obtain crystalline inorganic porous materials. The channel size and shape can be tuned by the composition and connectivity of cluster building units.6 Especially, this strategy can allow self-assembly to form crystalline mesoporous germanates up to 48-ring.7,8 Recently, borate compounds have received more and more interest for the following remarkable features: (1) A large number of B−O clusters ranging from [B2O5]4− to [B18O36]18− can be formed by the connection between BO3 and BO4;9−12 it is possible to obtain new B−O clusters/frameworks for their rich linking modes. (2) Borates are promising nonlinear optical materials; chiral open framework borates may obtained because BO3 rings contain asymmetric π-conjugated molecular orbitals.13,14 The SiO4/PO4 tetrahedra in aluminosilicate/aluminophosphate zeolites can be replaced by B−O cluster building units; these inorganic solids may exhibit regular pores of zeolites as well as nonlinear optical properties. Recently, a number of four-connected zeolite-type aluminoborates have been reported by Yang and co-workers.15,16 An illustrative example is BIT-1, which exhibits large 24-ring (24R) channels and an unusual zeolite CAN-type net constructed from alternately linked B5O10 clusters and AlO4 units; the SHG response of BIT-1 is a little larger than KDP (1.1 × KDP).17 In addition, the combination between B−O clusters can form open-framework boron oxides with pure B−O−B linkages.18,19 © 2017 American Chemical Society
Received: April 15, 2017 Published: June 7, 2017 6780
DOI: 10.1021/acs.inorgchem.7b00975 Inorg. Chem. 2017, 56, 6780−6783
Communication
Inorganic Chemistry
composed of B3O7 cluster units.27 In Na2Cs2Sr(B9O15)2, B9O19 clusters are formed by corner-sharing oxygen atoms of three B3O7 units; B9O19’s are further linked into a 3D network.28 We test second-order nonlinear optical properties of 1 for its polar space group P21 on a Q-switched Nd:YAG laser. The SHG signal intensity of 1 gradually increased with larger particle size, and it is phase-matchable. The SHG response of compond 1 is comparable to the KDP powder (Figure 3).29
Figure 1. (a) The B3O7 and B6O13 cluster units in 1. (b) View 9R and 13R channels along the b axis in 1. (c) Side view 13R channel with side pockets.
B3O7 and B6O13 clusters, in which odd 9R and 13R pores are observed along the b axis (Figure 1b). Interestingly, Na+ cations and H2O are appeared in the 9R and 13R channels, respectively (Figure S3). The diameters of 9R and 13R are about 5.10 × 8.73 Å and 8.81 × 9.77 Å, respectively. In addition, 9R windows are found perpendicular to the 13R channels. As a result, the whole open framework features an intersecting-channel system (Figures 1c, S4). The B−O and Na−O distances are similar to the known borates (Table S2). By excluding Na+ cations and H2O, compound 1 possesses 34.7% solvent-accessible volume via PLATON calculations. Compound 1 can be simplified as a 4,6-connected binodal net by assigning B3O7 and B6O13 clusters as nodes; the schläfli symbol is (44·62)(48·67) (Figure 2). The crystal structure of 1 is quietly different from known nonaborates. For example, LiBaB9O15, NaBaB9O15, LiSrB9O15, and NaK2B9O15 exhibit a 3D framework with channels
Figure 3. (Top) The SHG signals of 1 and KDP; (bottom) phasematching curve of 1.
Compound 1 has a UV cutoff edge of about 286 nm through the UV−vis−NIR diffuse reflectance spectrum (Figure S6), which suggests that 1 is a potential UV NLO material. The band gap is 4.29 eV calculated by Kubelka−Munk function (Figure S6).30 To better understand the structure−property relation and the origin of the SHG response, dipole moments were calculated to characterize the distortion of B−O groups, water molecules, and Na−O polyhedrons by using the density functional calculation at the B3LYP/3-21G level, as implemented in the Gaussian 03 program. Table 1 shows the calculated dipole moments of the BO 3 triangles, BO 4 tetrahedrons, water molecules, NaO 6 polyhedrons in Na2B9O15(H2O)(H3O), and the dipole moment of the unit cell. Obviously, the B−O groups and Na−O polyhedrons exhibit larger distortion measured by the nonzero dipole moment, which leads to the SHG response of 1. In summary, we successfully synthesized a chiral openframework boron oxide via solvothermal method by using 1,3-
Figure 2. View of the 4,6-connected binodal network in 1, in which the B3O7 and B6O13 clusters are shown as purple and green nodes. 6781
DOI: 10.1021/acs.inorgchem.7b00975 Inorg. Chem. 2017, 56, 6780−6783
Inorganic Chemistry
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Table 1. Dipole Moments (μ) of the BO3 Triangle, BO4 Tetrahedron, Water Molecules, and NaO6 Polyhedra in 1 μx
μy
μz
μtot
B(1)O3 B(2)O4 B(3)O4 B(4)O3 B(5)O4 B(6)O3 B(7)O3 B(8)O3 B(9)O4 Na(1)O6 Na(2)O6 H2O unit cell
−0.5327 1.9394 0.9099 0.7730 1.0924 −0.6468 −0.4299 1.5158 −0.0740 4.5803 0.0119 −0.7461 4.3556
−1.3875 1.7168 −0.9094 −0.1203 −0.7194 1.3433 −0.5263 −0.1181 −0.5388 −0.0352 2.1784 −1.3370 −7.5359
0.0085 0.3741 0.1501 0.0309 0.1259 0.0278 0.0316 0.0817 0.9925 1.1591 0.3126 0.1987 −20.3206
1.4863 2.6170 1.2952 0.7829 1.3140 1.4912 0.6803 1.5226 1.1317 4.7248 2.2008 1.5440 22.1062
diaminopropane as a solvent. Compound 1 can be reduced to a 4,6-connected binodal net by assigning B3O7 and B6O13 clusters as nodes. To the best of our knowledge, open-framework borates consisting of different cluster-building units are rarely observed. Powder SHG measurements indicate that compound 1 is type I phase-matchable, and the SHG efficiency is similar to KDP. Theoretical analyses reveal that the SHG response may from the synergistic effect of the π-conjugated systems of B−O groups and distorted NaO6 polyhedrons. We will explore new open-framework borates with large pores by using different oxoboron clusters as building blocks in future work.
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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.7b00975. X-ray crystallographic data, selected bond lengths, PXRD, UV/vis−NIR, IR, TGA, and additional structures (PDF) Accession Codes
CCDC 1551481 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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REFERENCES
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dipole moment (Debye) species
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AUTHOR INFORMATION
Corresponding Authors
*E-mail:
[email protected]. *E-mail:
[email protected]. ORCID
Jian-Wen Cheng: 0000-0002-7571-0096 Guo-Yu Yang: 0000-0002-0911-2805 Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS This work was supported by the NSFC (no. 21471130). 6782
DOI: 10.1021/acs.inorgchem.7b00975 Inorg. Chem. 2017, 56, 6780−6783
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DOI: 10.1021/acs.inorgchem.7b00975 Inorg. Chem. 2017, 56, 6780−6783
