Zeolitic Open-Framework Borates with Noncentrosymmetric Structures

Feb 13, 2019 - Three zeolitic pentaborates were directed by ethanediamine as structure-directing agents. The nonmetal-borate 1 features NCS layer, whi...
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Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX

Zeolitic Open-Framework Borates with Noncentrosymmetric Structures and Nonlinear Optical Properties Qi Wei,† Chao He,‡ Bang-Di Ge,† Meng-Xin Wan, Li Wei,*,† and Guo-Ming Wang† †

College of Chemistry and Chemical Engineering, Qingdao University, Shandong 266071, P.R. China College of Science, Hebei University of Science and Technology, Shijiazhuang, Hebei 050018, P.R. China

‡

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S Supporting Information *

ABSTRACT: Three zeolitic pentaborates (H2en)[B5O8(OH)] (1, en = ethylenediamine), (Hen)2[Al(B5O10)] (2), (H2en)[NH(CH3)2][Al(B5O10)] (3) were solvothermally obtained by employing ethanediamine molecules as structure-directing agents (SDAs). The nonmetal borate of 1 features a noncentrosymmetric two-dimensional layered structure. Through introducing Al atoms as the linkers and regulating the reaction conditions of 1, two three-dimensional zeolitic openframework aluminoborates, noncentrosymmetric (NCS) of 2 and centrosymmetric (CS) of 3, were achieved. Both 2 and 3 exhibit [Al(B5O10)]n2n− zeolitic frameworks based on the same fundamental building blocks (FBBs). However, the different arrangements between two FBBs result in 2 showing a NCS framework with dia topology, while 3 presents CS framework with cag topology. The flexibility of linkages modes of the FBBs as well as the unique structure-directing functions play crucial roles in the different formations. Powder second-harmonic generation (SHG) measurements revealed that acentric 1 and 2 possess nonlinear optical activity and 2 is type I phase-matchable with SHG responses of ∼1.0 time for KDP (KH2PO4). Infrared and UV−vis diffuse reflectance spectroscopy, along with electronic structure calculations, were also performed for the materials.

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INTRODUCTION Borates have attracted much research attention from scientists in inorganic chemistry and materials chemistry owing to their significant performance in nonlinear optical (NLO) and porous materials.1−24 Structurally, boron has the unique coordination modes of either triangular (BO3) or tetrahedral (BO4) geometries. They have no inversion centers and tend to polymerize into a great variety of oxoboron polyanionic units.3,25−29 The diverse clusters increase the likelihood of creating new structures which can be functionalized for targeted applications. The crystallographic feature makes borates possess a higher tendency to crystallize in the asymmetric space group, more than 35% of known borates are featured with asymmetric structures compared to the average value of 15% for inorganic crystals.12,30,31 Furthermore, the BO3 planar unit with a πconjugated system possesses a relatively large microscopic NLO susceptibility. The B−O bond has no absorption in the ultraviolet region owing to the large covalent bond energy. All the unique structural features render borates attractive candidates for making desired UV NLO materials. For example, the excellent materials, β-BaB 2 O 4 (BBO) 32 and LiB 3 O 5 (LBO),33 are commercially available as NLO devices. The oxoboron polyanionic clusters are usually arranged orderly, giving rise to supermolecular assemblies via hydrogenbond interactions. In order to construct extended structures, introducing heteroatoms as the linking centers into nonmetal borate backbones for generating extended structures has resulted in several intriguing systems, such as borophosphates,34,35 borogermanates,36−40 and vanadoborate.41−43 Re© XXXX American Chemical Society

cently, Al atoms have been successfully introduced into the borate system, giving rise to a new family of aluminoborates (ABOs) NLO materials.7,44−50 The tetrahedral coordination of Al3+ ions links with the acentric polyborate clusters via covalent bonds, generating the rigid extended solid structures. Therefore, it is highly expected that ABOs can aggregate zeolitic porosity with the desirable optical behaviors of borate materials. For example, [Zn(1,3-diaminopropane)2][AlB5O10] consists of the characteristics of both zeolitic inorganic architecture and a metal−organic coordination network, displaying a fourconnected diamond (dia) topology.7 BIT-1 possesses a threedimensional (3-D) zeolite net and exhibits the largest pores in aluminoborates.45 [Zn(1,3-diaminopropane)2][AlB5O10] and BIT-1 exhibit moderate SHG efficiency of ∼1/3 and ∼1.1 times that of KDP (KH2PO4), respectively. Here, as our ongoing exploration of this theme, using ethylenediamine as structure-directing agents (SDAs), three borates containing pentaborate (B5O10) clusters have been achieved. The noncentrosymmetric (NCS) nonmetal borate of 1 features a two-dimensional (2-D) layered structure. Two 3-D zeolitic ABOs of 2 and 3 exhibit [Al(B5O10)]n2n− openframeworks, but 2 shows NCS structure with dia topology, while 3 presents centrosymmetric (CS) framework with cag topology. NLO determination revealed that 2 represents moderate SHG response of ∼1.0× KDP and is phase matchable. Received: January 11, 2019

A

DOI: 10.1021/acs.inorgchem.9b00101 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry

expressed briefly here. 1 belongs to NCS space group Cc (Table 1). Its asymmetrical unit contains a [B5O8(OH)] (B5-I) cluster

Infrared and UV−vis diffuse reflectance spectroscopy as well as theoretical calculations are also presented.

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Table 1. Crystallographic Data and Structure Refinements for 1−3

EXPERIMENTAL SECTION

Related Materials and Instruments. The elemental analysis data were determined using a PE2400 II analyzer. Powder XRD measurements were carried out by a Rigaku MiniFlex II diffractometer. Thermogravimeric analyses (TGA) were obtained with a Mettler Toledo TGA 1100 analyzer. Infrared spectra analyses were performed on a TENSOR 27 spectrometer. UV−vis diffuse reflectance spectral data (200−800 nm) were collected using a Rigaku UV-3100 spectrophotometer with BaSO4 as the standard. Second-Harmonic Generation Measurements. Powder SHG measurements were carried out on a Q-switched Nd:YAG solid-state laser.51−53 The samples were ground and sieved through a series of mesh: ≤45, 45−58, 58−75, 75−109, 109−150, 150−212, and 212− 270 μm. The NLO material of crystalline KDP with the identical fashion was utilized as the reference. Structural Determination. The diffraction data collection was performed on a Gemini A Ultra diffractometer for 1 and 2, and XtaLABmini diffractometer for 3 with Mo Kα radiation (λ = 0.71073 Å) at 293 K. The structures were solved with SHELX-2014 program.54 The nonhydrogen atoms were anisotropically refined. The positions of all H atoms were generated geometrically. They were verified by the ADDSYM algorithm,55 and no higher symmetry was discovered. CCDC 1879752 (2) and 1879753 (3). Theoretical Calculations. The electronic property calculation was performed based on density functional theory (DFT).56,57 To manage the interaction between ions and electrons precisely, optimized ultrasoft-pseudopotentials are selected. These electronic configurations were treated as valence electrons: for 1: B 2s22p1, C 2s22p2, H 1s1, O 2s22p4, and N 2s22p3; for 2: B 2s22p1, C 2s22p2, N 2s22p3; O 2s22p4, H 1s1, and Al 3s23p1. In addition, for plane wave basis cut off energy, the Ecutoff = 370.0 eV was employed.

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compds

1

2

3

empirical formula formula weight crystal system space group a [Å] b [Å] c [Å] β [o] V [Å3] Z Dc [g cm−3] μ [mm−1] F(000) refl. collected independent refl. GOF on F2 R1, wR2 (I > 2σ(I))a R1, wR2 (all data) Flack parameter peak/hole [e A−3]

C2N2H11B5O9

C4N4H18AlB5O10

C4N3H17AlB5O10

261.18 monoclinic Cc 6.7048(4) 11.4412(6) 12.5266(8) 95.413(6) 956.65(10) 4 1.813 1.454 536 2833 1443

363.25 monoclinic P21 8.7494(10) 9.9042(9) 9.1007(8) 109.363(11) 744.02(14) 2 1.621 0.194 376 3417 2127

348.23 orthorhombic Pbca 12.9221(11) 13.0596(9) 17.5423(12) 90.00 2960.4(4) 8 1.63 0.190 1440 7513 2606

1.060 0.0366, 0.0843

1.135 0.0662, 0.1917

1.054 0.0602, 0.1734

0.0430, 0.0901

0.0718, 0.1981

0.0758, 0.1891

0.50 0.183/−0.227

0.3(2) 0.876/−0.598

− 0.565/−0.636

R1 = ∑||F o| − |Fc||/∑|F o|, wR 2 = {∑w[(F o)2 − (Fc)2]2/ ∑w[(Fo)2]2}1/2.

a

RESULTS AND DISCUSSION and a discrete (H2en)2+ cation (Figure 1a). Based on the calculated bond valence −1.02 for O(9) as well as the requirement of charge balance, atom O(9) is assigned to a hydroxyl group. The fundamental building blocks (FBBs) of the

The layered nonmetal borate of 1 and 3-D aluminoborates of 2 and 3 were all made by solvothermal reactions. The phase purity of these samples was affirmed by EA data and PXRD determination (Figure S1, Supporting Information). 1 features a layered structure constructed by [B5O8(OH)] clusters. The terminal OH groups of pentaborate clusters prevent the layers from further connections. It is believed that increasing the basicity may be an effective method to preventing the protonation of the oxoboron units.17,44,58 In addition, the metal atom exhibits flexible coordination geometries, providing freedom in generating novel borates with intriguing structures and potentially interesting structure-related physicochemical properties. Inspired by these ideas, by introducing Al atoms to the reaction system, two 3-D aluminoborates were realized. It is noteworthy that the pH value indeed has a vital influence on the resultant products. When the volume of en is 0.5 mL with the mixed solvent of 1.0 mL H2O and 1.0 mL pyridine, the layered 1 was obtained. Increasing the volume of en (2.0 mL) in the solvent of 1.0 mL ethyl alcohol mixed with 2.0 mL pyridine for 2 and 3.5 mL N,N-dimethylformamide for 3 makes two 3-D aluminoborates. This investigation indicates that regulating the pH values is an effective way for generating novel borates under solvothermal conditions. Moreover, the structural evolution from 2-D layers of 1 to the 3-D open-framework of 2 and 3 indicates the important role the metal atom played. Meanwhile, these results further impress the significance of structural engineering on designing desirable materials. Structure of (H2en)[B5O8(OH)] (1). The structure of 1 has been reported in 2007,59,60 and the structural delineations are

Figure 1. (a) The asymmetric unit of 1. (b) View of the layer along the c-axis. (c) View of the arrangement of the layers in the -LLL- sequence along the b-axis. (d) View of the topological network. Color code: BO3 triangle, cyan; BO4 tetrahedron, yellow. B

DOI: 10.1021/acs.inorgchem.9b00101 Inorg. Chem. XXXX, XXX, XXX−XXX

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Figure 2. (a) The asymmetric unit of 2. (b) Polyhedral view of the 3-D framework with 11-MR along the a-axis. (c) View of the topological network. (d−f) View of the 3-D framework with 6L and 8R helical channels along the b-axis. Color code: B5-II cluster, cyan; AlO4 tetrahedron, purple.

helices and the left(L)-handed 6-MR helices. In addition, viewing along the a-axis, the network exhibits straight channels with 11-MR windows (the diameter of ∼9.2 × 9.5 Å2 without considering internal van der Waals radii (similarly hereinafter)). Two independent (H2en)+ are precisely located in the 11-MR channels, connecting with the anionic network with hydrogenbonding interactions (Table S2, Figure S2b). Structure of (H2en)[NH(CH3)2][Al(B5O10)] (3). 3 belongs to a CS space group Pbca (Table 1). In its asymmetric unit, there is one Al3+, one [B5O10] (B5-II) cluster, one guest [NH(CH3)2], and one (H2en)2+ cation (Figure 3a). The [NH(CH3)2] units are resulted from in situ hydrolysis of N,N-dimethylformamide.66 Al3+ ion also adopts tetrahedral geometry (Al−O: 1.706(2)−1.720(2) Å). 2 and 3 possess the same FBBs, but the different linkage modes of the FBBs lead to two kinds of architectural frameworks. Different from the acentric dia-type network of 2, in which every B5-II cluster links to 12 others via 4 neighboring AlO4 groups and vice versa, in 3, every B5-II cluster links 11 other ones through 4 linking AlO4 groups and vice versa, resulting in a centric [Al(B5O10)]n2n− framework with CaGaO2 (cag) topology (Figure 3). The CS framework likewise possesses intersecting channels. Viewing along the a-axis, the framework shows the layers with 8- and 14-MR windows (the diameter of ∼5.8 × 8.2 Å2/8MR and ∼7.6 × 15.2 Å2/14MR, Figure 3b). Unfortunately, the neighboring layered structures are arrayed with an -AA′A- sequence, so the channels are interruptive owing to the symmetry operation (Figure 3d). The coupled [H2(en)]2+ and [NH(CH3)2] reside in the 14-MR channels and interact with the inorganic network via hydrogen bonds. Interestingly, the layers which contain 8- and 14-MR windows were also found in [H2TETA]AlB5O10 (3a, TETA = triethylenetetramine) and [CH3NH3][CH3CH2NH3](H2O)2[Al(B5O10)] (3b).23,24,67 However, the layers in 3a and 3b overlap to form straight 8-, 14-MR channels, and both structures exhibit SrAl2 (sra) topology. Besides, the structure of 3 also possess layers with

B5-I cluster can be simplified as 3Δ2□:⟨2Δ□⟩-⟨Δ2□⟩ (Δ, BO2(O/OH) triangles; □, BO4 tetrahedra) according to the descriptor proposed by Burns et al.61 Each B5-1 FBB is connected, neighboring four others and resulting in a [B5O8(OH)]n2n− anionic layer with nine-membered rings (9MR) (Figure 1b). TOPOS analysis62 indicates that the single layer could be regarded as a sql topology (Figure 1d). Alternatively, the anionic layer could also be seen as the BO2(OH) groups hanging on one side of the 2-D structure. Thus, it is clear that the layer is asymmetric (Figure 1c). These asymmetric layers feature a parallel arrangement with all terminal hydroxyl units directing toward the same direction, which results in the highly polar structure. (H2en)2+ cations lie in the interlayer and are linked to the inorganic structure with multipoint N−H···O hydrogen bonds (Table S2, Figure S2a), directing the whole NCS structure of 1. Structure of (Hen)2[Al(B5O10)] (2). 2 belongs to chiral space group P21 (Table 1). There is one Al3+ ion, a [B5O10] (B5II) cluster, and two guest (Hen)+ cations in its asymmetric unit (Figure 2a). B5-II FBB can be represented as a shorthand notation of 4Δ1□:⟨2Δ□⟩-⟨2Δ□⟩ in terms of the classification of polyborates. Al atom is tetrahedrally coordinated, forming to AlO4 group with an Al−O distance ranging from 1.729(6) to 1.743(6) Å. In addition, the B−O distance spans from 1.332(10) and 1.477(9) Å. All the values are in accord with the reported ones.7,10,11,45,46,63 The strict alternation between B5-II cluster and AlO4 groups via the vertices generates a 3-D [Al(B5O10)]n2n− anionic zeolitic framework (Figure 2b).64,65 When B5-II and AlO4 FBBs were simplified to four-connected nodes, the structure featured a dia topology (Figure 2c). In detail, the structure possesses types of unidimensional channels running along different directions, in which the unclosed 8- and 6-MR channels are helical along the baxis (Figure 2d−f). Both the 8- or 6-MR helical channels display one type of chirality, respectively: the right(R)-handed 8-MR C

DOI: 10.1021/acs.inorgchem.9b00101 Inorg. Chem. XXXX, XXX, XXX−XXX

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hydrogen-bonding interactions have a significant effect on the macroscopic centricities of these structures. In 1, the adjacent [H2(en)]2+ cations are arrayed parallelly along the b-axis and directed along the same direction along the c-axis. The cations interact with inorganic layers through hydrogen-bonding interactions, making the layers uniformly arranged in the same directions and giving rise to the highly polar structure (Figure 1c, Figure S2a). For 2, two independent (H2en)+ cations are arranged in the same directions uniformly along the b-axis. The local acentric feature is constructively transformed to inorganic framework, which is the determining factor for the acentricity of the structure of 2 (Figure 2b, Figure S2b). In 3, either [H2(en)]2+ or [NH(CH3)2] units are coupled, located in the 14-MR channels with an inversion center, respectively. They are bonded to inorganic framework through the perfectly symmetrical hydrogen-bonding interactions. As a result, the polarities around the channels are completely canceled out. The structural feature is further transferred to the extended framework, rendering compound 3 CS structure (Figure 3b, Figure S2c). Hence, it is believed that there is a good symmetry correspondence between the arrangements of the SDAs and the host frameworks.68−70 Obviously, hydrogen-bond interactions between the guest SDAs and the host frameworks play an important role on the formations and the macroscopic centricities of 1−3. Optical Properties. The IR spectra are shown in Figure S3. The broad bands around 3400−3180 cm−1 and 1630−1597 cm−1 are likely the stretching and bending vibrations of N−H and C−H bonds, respectively. All of the three spectra exhibit similar B−O vibrations for BO3 and BO4 groups. However, for aluminoborates 2 and 3, the absorption bands around 510 and 440 cm−1 can be attributed to stretching−bending vibrations of AlO4 units.71,72 These results are in accordance with the structural analyses. The optical diffuse reflectance spectra are shown in Figure 4. The absorption spectra were converted by the Kubelka−Munk function of α/S = (1 − R)2/2R (α is the absorption coefficient, S is the scattering coefficient, and R is the reflectance).73 From the α/S versus E plots, the optical band gaps are obtained with values of ∼4.89, ∼5.73 and ∼5.54 eV, consistent with UV cut off edges at ∼254, ∼216 and ∼223 nm for 1−3, respectively. It is noteworthy that the values are comparable to the band gaps of other aluminoborates directed by organic amine cations, such as [H3(N,N′-bis(3-aminopropyl)ethylenediamine)]6[Al(B5O10)]· (5.59 eV),23 12H2O [CH3NH3]1.5[CH3CH2CH2NH3]0.5(H2O)5[Al(B5O10)] (5.92 eV), 45 and[CH 3 NH 3 ][CH 3 CH 2 NH 3 ](H 2 O) 2 [Al(B 5 O 10 )]

Figure 3. (a) The asymmetric unit of 3. (b, c) Polyhedral view of the 3D framework along the a-axis and b-axis, respectively. (d, e) View of the topological network the a-axis and b-axis, respectively.

11-MR windows (the diameter of ∼9.4 × 10.4 Å2, Table S2, Figure S2c). Due to the reversion and the translation, the layers are also stacked with a -BB′B- sequence along the b-axis (Figure 3c,e). Structure Relations. Although all three materials are directed by ethanediamine molecules, they represent distinctly different structures. Non-metal borate of 1 features an acentric layered network. Through introducing Al atoms to the reaction system, two 3-D aluminoborates were achieved. Although both 2 and 3 exhibit [Al(B5O10)]n2n− zeolitic open-frameworks based on the same FBBs of pentaborate (B5O10) clusters and AlO4 tetrahedra, they exhibit the distinct centricities: 2 exhibits a NCS network with dia topology, while 3 displays a CS skeleton with cag topology. The host−guest symmetry matching as well as

Figure 4. UV−vis−NIR diffuse reflectance spectra and absorption spectra of compounds 1−3. D

DOI: 10.1021/acs.inorgchem.9b00101 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry (5.70 eV),67 indicating that 1−3 are wide-band gap semiconductors. Nonlinear Optical Property. NCS structures of 1 and 2 prompted us to investigate their NLO behavior. The SHG tests of the powder samples were performed employing a Nd:YAG laser (1064 nm as the fundamental frequency light). As illustrated in Figure 5, the results indicate that 1 and 2 show

Figure 5. Oscilloscope traces of SHG signals of the powder of KDP and compounds 1 and 2 (left). Phase matching curve (particle size versus SHG intensity data for 2 (right)).

SHG intensities of ∼0.6 and ∼1.0 times that of KDP in the same particle size of 150−212 μm, respectively. Based on the rule proposed by Kurtz and Perry, the plots of SHG intensities versus particle sizes reveal that compound 2 is type-I phase-matching.51 The moderate SHG response as well as the short cutoff edge make 2 a potential UV NLO material. Theoretical Calculations. To get an in-depth understanding the electronic properties, theoretical calculations were performed based on density functional theory.56 Theoretical result reveals that both 1 and 2 are direct band gap materials because the valence band maximum (VBM) and the conduction band minimum (CBM) are localized at the same points, respectively (Figure S5). As shown in Figure 6, the bands can be assigned according to the total and partial density of states. For 1, the VBs between −8.0 and −4.0 eV are mainly formed by N 2p, C 2p, and O 2p states. The top part of the VB (−4 to 0 eV) is constituted of O 2p with small amounts of B 2p states, while the VB minimum mainly originates from B-2p along with small amounts of C 2p and H 1s states. For 2, the VBs between −8.0 and −4.0 eV are attributed to O 2p, C 2p, and B 2p states. In the range from −4 to 0 eV, the VBs are dominanted by O 2p and N 2p states. The mixing of B 2p and C 2p states and small amounts of Al 3p and H 1s states makes up the bottom of the CB. According to the analyses, it is considered that the anionic oxoboron groups predominately determine the energy bandgaps and optical properties of 1 and 2.

Figure 6. Total density of states and partial density of states of compounds 1 and 2.

framework with cag topology. The flexibility of linkages modes of the FBBs as well as the unique structure-directing functions play crucial roles in the different formations. UV−vis spectroscopy suggests that the materials are wide-band gap semiconductors. NLO determination revealed that acentric 1 and 2 possess efficient SHG. 2 possesses a SHG coefficient comparable to that of KH2PO4 and is type I phase matchable. These features endow 2 with a potential application as an UV NLO material. The study indicates that the solvothermal technique combined with organic amines as SDAs is conducive to exploring novel borates, which offers the potential for exploring new NLO materials.

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CONCLUSIONS In summary, three zeolitic pentaborates have been solvothermally obtained and characterized. Although all of materials are directed by ethanediamine molecules, they represent distinctly different structures, revealing the unique structure-directing ability of organic templates in building borates. The nonmetal borate of 1 features an acentric [B5O8(OH)]n2n− 2-D structure. On the basis of 1, through introducing Al atoms in the reaction system, two 3-D zeolitic aluminoborates were achieved. Both 2 and 3 exhibit [Al(B5O10)]n2n− open-frameworks, but 2 shows a NCS structure with dia topology, while 3 presents a CS

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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.9b00101. X-ray crystallographic file in CIF format, simulated and measured powder XRD patterns, IR spectra, TGA, and additional structures (PDF) E

DOI: 10.1021/acs.inorgchem.9b00101 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry Accession Codes

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CCDC 1879752−1879753 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 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

Guo-Ming Wang: 0000-0003-0156-904X Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by grants from the Natural Science Foundation of China (21701094, 21571111) and the Natural Science Foundation of Shandong Province (ZR2018BB003).

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DOI: 10.1021/acs.inorgchem.9b00101 Inorg. Chem. XXXX, XXX, XXX−XXX