Centrosymmetric (Hdima)2[Ge5B3O15(OH)] and Noncentrosymmetric

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Cite This: Inorg. Chem. 2017, 56, 12695-12698

Centrosymmetric (Hdima)2[Ge5B3O15(OH)] and Noncentrosymmetric Na4Ga3B4O12(OH): Solvothermal/Surfactant-Thermal Synthesis of Open-Framework Borogermanate and Galloborate Su-Juan Yu,† Xiang-Yu Gu,† Ting-Ting Deng,† Jian-Hao Huang,† 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 *

reported. The Zhao and Mao groups reported a series of inorganic alkaline/alkaline-earth-ion-templated BGOs by using low-temperature flux and high-temperature solid-state methods.17−19 CsGeB3O7 and Cs2GeB4O9 exhibited two different 4connected 3D networks, in which B3O7/B4O9 linked with GeO4. The SHG responses of the two compounds are about 1.5 and 2.8 KH2PO4 (KDP), respectively. In a comprehensive review, Mao et al. summarized the B−O and Ge−O building units, structural features, and nonlinear-optical (NLO) properties of the reported BGOs.22 These BGOs can be classified as B- and Ge-rich materials with different Ge/B ratios, and the Ge/B ratios are responsible for the distinct connectivity modes and final structures of the BGOs. Ga3+ has the same coordination geometries (GaO4, GaO5, and GaO6) as Ge4+ and shows an outer electronic configuration similar to that of B3+. Compared with a large number of aluminoborates,24 only several limited examples of 3D openframework galloborates (GBOs) have been synthesized via the solvothermal and boric acid flux methods,25 K2[Ga(B5O10)]· 4H2O is the first zeolite-type GBO; 11R channels are built by GaO4 and B5O10 units.25a The 18R channels of Ga-PKU-1 consist of 18 edge-sharing GaO6 octahedra; the B−O units just act as terminal groups.25c Developing new synthetic methods continues to be of great importance in this field. Recently, Zhang and co-workers developed a new method to prepare crystalline inorganic materials by using various surfactants as solvents.26 If a surfactant-thermal process is introduced, new open-framework borates may be formed that are different from those of other synthetic methods and would offer more chances for synthesizing new borates. To the best of our knowledge, there are no reports of microporous metal borates prepared by using surfactants as solvents. Recently, we reported a zeolite sodalite-type BGO, CsBxGe6−xO12 (x = 1),23 and a layered open-framework GBO, Ba3Ga2[B3O6(OH)]2[B4O7(OH)2],27 under solvo/hydrothermal conditions. This Ge-rich BGO exhibits a mixed Ge4+/B3+ site and the highest Ge/B up to 5:1 than previously reported BGOs, while GBO shows a 3D porous layer structure with 14R channels along different directions. In this study, we obtained two new

ABSTRACT: Under solvothermal/surfactant-thermal conditions, two new open-framework borogermanate and galloborate, centrosymmetric (Hdima)2[Ge5B3O15(OH)] (1; dima = dimethylamine) and noncentrosymmetric Na4Ga3B4O12(OH) (2), were obtained and characterized. Compound 1 contains an unusual basket-shaped Ge5B3O18(OH) cluster and displays a 3D open-framework layered structure. Compound 2 shows an interrupted 3,4connected network constructed by alternately linked BO3 units and Ga3+ ions and displays weak second-harmonicgeneration response.

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rystalline open-framework borates and germanates are important types of inorganic microporous materials for their rich architectures and potential applications.1−5 In contrast to TO4 tetrahedra in aluminosilicate and aluminophosphate zeolites, B and Ge atoms show flexible coordination geometries such as BO3, BO4, GeO4, GeO5, and GeO6 and are likely to form various B−O and Ge−O clusters with different sizes.6−10 Particularly, these clusters can be further assembled into openframework solids with micropores and even mesopores.11−14 A notable example is Na2B9O15(H2O)(H3O); the connection between the B6O13 and B3O7 clusters gives a 4,6-connected net with 13-ring (13R) micropores, which have shown moderate second-harmonic-generation (SHG) response.11 Several crystalline mesoporous germanates are prepared by introducing larger building units. The 48R mesopores of PKU-17 are made by the combination of Ge7 and Ge10 clusters, and PKU-17 shows a good selective CO2 adsorption property.14b The highly open-framework germanates are attributed to the smallest 3Rs in germanates, which are due to the smaller Ge−O−Ge angles and longer Ge−O bonds. The incorporation of B−O and Ge−O groups into the same framework leads to a new type of inorganic solid, borogermanate (BGO).15−23 To date, different synthetic methods have been used to synthesize various BGOs. For example, Zou, Yang, and co-workers systematically investigated organically templated BGOs by using the solvothermal method.15,16 (C4N3H15)[(BO2)2(GeO2)4] is the first organically templated BGO that contains intersecting 8R and 12R channels built by B2O7 and Ge8O24, and the unusual zeolite topology has never been © 2017 American Chemical Society

Received: September 9, 2017 Published: October 18, 2017 12695

DOI: 10.1021/acs.inorgchem.7b02328 Inorg. Chem. 2017, 56, 12695−12698

Communication

Inorganic Chemistry

contains intersecting 8R and 9R channels constructed by B4O8(OH) units and GeO4 tetrahedra.17b Surfactant-thermal reactions of NaBO2·4H2O (2 mmol, 0.308 g), Ga2O3 (0.5 mmol, 0.094 g), dimethylamine (1 mL), and poly(ethylene glycol)-200 (5 mL) at 170 °C for 6 days produce colorless cubic crystals of 2 (see the Supporting Information). 2 could not be prepared if using water or other organic amines as reaction media under similar conditions. Compound 2 crystallizes in the noncentrosymmetric cubic space group F4̅3c.28 The asymmetric unit of 2 contains one Ga, one B, two Na, and two O atoms. The Ga atom is tetrahedrally coordinated with an average Ga−O distance of 1.83 Å, while the B atom is triangularly coordinated with a B−O distance of 1.38 Å for the BO3 group, which are similar to the reported results (Table S4). As shown in Figure 2a, six Ga3+ ions are linked by four BO3

BGO and GBO, (Hdima)2[Ge5B3O15(OH)] (1; dima = dimethylamine) and Na4Ga3B4O12(OH) (2), under solvothermal/surfactant-thermal conditions. Compound 1 features a 5connected 3D open-framework layered structure composed of unique basket-shaped Ge5B3O18(OH) clusters, while compound 2 contains a cagelike framework built by alternately linked BO3 units and Ga3+ ions. X-ray crystallographic data are given in CIF format for 1 (CCDC 1568830) and 2 (CCDC 1571148). Solvothermal reactions of GeO2 (1 mmol, 0.1046 g), H3BO3 (10 mmol, 0.6183 g), N,N-dimethylacetamide (5 mL), and dimethylamine (1 mL) at 170 °C for 6 days produce colorless crystals of 1 (see the Supporting Information). Compound 1 crystallizes in the centrosymmetric triclinic space group P1;̅ 5 Ge, 3 B, and 16 O atoms and 2 [Hdima]+ ions are found in the asymmetric unit.28 The B−O and Ge−O bond lengths are similar to those of reported BGOs (Table S2). Two BO4 tetrahedra and one BO2(OH) triangle are connected by corner-sharing O atoms to give a B3O7(OH) cluster. The B3O7(OH) cluster connects five corner-sharing GeO4 tetrahedra to give a unique basket-shaped Ge5B3O18(OH) cluster (Figure 1a). This type of cluster is first

Figure 2. (a) Ga6(BO3)4 cage in 2. (b) Cubic cavity (yellow ball) constructed from eight Ga6(BO3)4 cages (purple balls). (c) View of the channels along the a axis.

triangles to form a novel octahedral Ga6(BO3)4 cage; this kind of cage has not been observed in borate chemistry. Each Ga6(BO3)4 unit connects six other neighboring units by sharing Ga3+ ions and finally forms the whole 3D chiral GBO framework; 8R channels are found running along the [100], [010], and [001] directions (Figure 2c). Notably, this cubic cavity is built by eight Ga6(BO3)4 units, in which guest Na+ and OH− ions are located; the diameter is about 6.83 Å (Figure 2b). Each BO3 is linked to three GaO4, and each GaO4 is linked to four BO3; the whole framework exhibits a 3,4-connected net with the Schläfli symbol of (63)4(62·84)3 (Figures 3b and S2). Ion-exchange experiments show that Na+ ions cannot be exchanged with Li+, NH4+, K+, and Rb+ ions. The IR spectrum clearly confirms the presence of OH groups and BO3 units in 2; no stretching and bending bands of BO4 have been observed, which is consistent with the crystal

Figure 1. (a) Basket-shaped Ge5B3O18(OH) cluster in 1. (b) View of 10R channels along the c axis in 1. (c) View of 8R channels along the b axis in 1.

observed in BGOs. Each Ge5B3O18(OH) cluster connects with five nearest neighbors via Ge−O−Ge bonds to give the final 5connected layered anionic open framework, in which 6R, 8R, and 10R pores are found along three different directions (Figures 1b,c, 3a, and S1). The guest [dima]+ cations are found in the layers and adjacent layers and interact with the framework with strong hydrogen bonds (Table S3). This type of 3D microporous layer was first observed in AMH-3; this layered silicate shows 8R pores along three different directions.29 The only example of 3D open-framework layered BGO is K4[B8Ge2O17(OH)2], which 12696

DOI: 10.1021/acs.inorgchem.7b02328 Inorg. Chem. 2017, 56, 12695−12698

Communication

Inorganic Chemistry

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] (J.-W.C.). *E-mail: [email protected] (G.-Y.Y.). ORCID

Jian-Wen Cheng: 0000-0002-7571-0096 Guo-Yu Yang: 0000-0002-0911-2805

Figure 3. 5- and 3,4-connected networks for 1 (a) and 2 (b).

Notes

structure results (Figure S3). To the best of our knowledge, open-framework metal borates constructed by corner-sharing BO3 units and metal ions are not reported because the oxo boron clusters easily formed under hydro/solvothermal conditions. Powder X-ray diffraction (PXRD) data indicate the phase purities of 1 and 2 (Figure S4). The band gaps are 5.6 and 4.9 eV for 1 and 2, respectively, via UV−vis diffuse-reflectance spectra (Figures 4a and S6). Compound 2 shows a very weak SHG

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by the National Science Foundation of China (Grant 21471130).

Figure 4. (a) Optical diffuse-reflectance spectra for 1 and 2. (b) Emission spectrum of 2.

response of ∼0.1KDP via NLO measurement under a 1064 nm laser beam (Figure S7). The weak SHG response may be due to the arrangement of BO3 units in an unfavorable manner. When excited at 277 nm, compound 2 emits blue luminescence with strongest emissions at 515 nm (Figures 4b and S8), and the decay lifetime is 22.65 ns. In summary, we synthesized a new organically templated BGO 1 and alkali-metal GBO 2 under solvothermal/surfactantthermal conditions. BGO shows 3D open-framework layers constructed by new basket-shaped Ge5B3O18(OH) clusters, while GBO contains a novel octahedral Ga6(BO3)4 cage and exhibits an interrupted 3,4-connected network. GBO exhibits a weak SHG response and blue luminescence. Our studies indicate that a surfactant-thermal method is an effective approach to preparing novel open-framework metal borates. Further work on this subject is in progress.

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REFERENCES

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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.7b02328. X-ray crystallographic data, selected bond and hydrogenbond lengths, PXRD, IR, TGA, UV−vis, SHG signals, excitation spectra, and additional structures (PDF) Accession Codes

CCDC 1568830 and 1571148 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 12697

DOI: 10.1021/acs.inorgchem.7b02328 Inorg. Chem. 2017, 56, 12695−12698

Communication

Inorganic Chemistry

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DOI: 10.1021/acs.inorgchem.7b02328 Inorg. Chem. 2017, 56, 12695−12698