Galloborate Frameworks Templated by Organic

Article Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX

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Three Alumino/Galloborate Frameworks Templated by Organic Amines: Syntheses, Structures, and Nonlinear Optical Properties Lin Cheng†,‡ and Guo-Yu Yang*,† †

MOE Key Laboratory of Cluster Science, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081, China ‡ College of Chemistry, Tianjin Normal University, Tianjin 300387, China

Inorg. Chem. Downloaded from pubs.acs.org by UNIV OF NEW ENGLAND on 10/10/18. For personal use only.

S Supporting Information *

ABSTRACT: A series of alumino/galloborates, including (H 3 APEA) 6 [Al-B 5 O 10 ] 9 ·12H 2 O (1, APEA = N,N′-bis(3aminopropyl)ethylenedi-amine), (HDETA)2(H2DETA)2[AlB5O10]3 (2, DETA = diethylenetriamine), and (H2EDAP)[GaB5O10]·H2O (3, EDAP = N-ethyl-diaminopropane), was solvothermally synthesized and characterized in solid-state by powder X-ray diffraction, Fourier transform infrared spectroscopy, UV−vis spectroscopy, and single-crystal X-ray diffraction. All of them feature the [MB5O10]n2n− (M = Al or Ga) frameworks, charge-balanced by the long chain-like amine cations. Three frameworks exhibit different interlinkage modes of {MB5O10} layers, resulting in channels varying in size and shape. The flexibility of long chain-like amine cations as well as their significant structure-directing functions in forming these crystalline products is also discussed in detail. Powder second-harmonic generation measurements showed that all three compounds present a nonlinear optical property, and compound 2 exhibits type I phase-matchable optical nonlinearity.

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INTRODUCTION Nonlinear optical (NLO) materials have been widely investigated for their applications in laser technology.1 As a significant subclass of NLO materials, borates have attracted a lot of research attention owing to their higher trend to crystallize in the acentric space group (∼36%) compared to the average level for other inorganic materials (∼15%).1a This crystallographic feature stems largely from the diversity and acentric nature of the boron-oxo clusters built by two types of coordination modes: BO3 trigonal plane and BO4 tetrahedron.2 As a typical weak Lewis acid, boric acid tends to undergo the condensation to form borate clusters,3 such as the prevalent B4O94 and B5O10.5 These discrete clusters, featuring various nuclearities and architectures, are usually arranged orderly in the crystal lattice and interact with each other through weak hydrogen bonds to form supermolecular assemblies. In recent years, the Al3+/Ga3+ ions have been successfully introduced into the synthesis of polyborate,6 resulting in a new class of alumino/galloborate (ABO/GBO) NLO materials. First, the Al3+/Ga3+ ions can connect with the acentric polyborate anions through covalent Al/Ga−O bonds, giving rise to the rigid extended solid structures. Second, the tetrahedral coordination of Al3+/Ga3+ by diversified polyborate groups benefits the formation of chiral sites in the solid structure. Third, the Group IIIA metal ions that are favorable for the transmission of UV light ensure the wide absorption window requirement of NLO crystals. The [MB5O10]n2n− (M = Al or Ga) frameworks possess a rich isomerism;6b,7 nevertheless, this has not been investigated © XXXX American Chemical Society

on a detailed level. The structure-directing roles of different organic templates, e.g. amine and alkali cations, can not only force the B5O10 cluster to create distortions but also diversify their connection to Al3+/Ga3+ ions, enriching the overall structural variety. Long chain-like amines exhibit softness and flexibility because of their free rotation of C−C or C−N bonds, as discussed in a recent review article.8 In this work, we present the successful use of chain-like amines as structure-directing agents (SDAs) in building a series of ABO/GBO compounds, namely, (H3APEA)6[AlB5O10]9·12H2O (1, APEA = N,N′bis(3-aminopropyl)ethylenediamine), (HDETA)2(H2DETA)2[AlB5O10]3 (2, DETA = diethylenetriamine), and (H2EDAP)[GaB5O10]·H2O (3, EDAP = N-ethyl-diaminopropane). Three compounds possess the isomeric inorganic frameworks with the same stoichiometry of [MB5O10]n2n−. By virtue of systematic structural analysis, we provide a deep insight into this isomerism and reveal the complicated relationship between long chain-like amines and ABO/GBO frameworks.

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EXPERIMENTAL SECTION

Materials and Methods. All chemicals used in this study were analytical grade and used directly. Elemental analysis (C/H/N) was done using a German Elementary Vario EL III instrument. The solidstate UV−vis spectra were obtained at room temperature using a PE Lambda 950 UV−vis spectrophotometer, and a BaSO4 plate was Received: July 27, 2018

A

DOI: 10.1021/acs.inorgchem.8b01925 Inorg. Chem. XXXX, XXX, XXX−XXX

Article

Inorganic Chemistry Table 1. Crystallographic Data for 1−3 identification code empirical formula formula weight temperature (K) wavelength (Å) crystal system, space group a (Å) b (Å) c (Å) α (deg) β (deg) γ (deg) volume (Å3) Z, calculated density (Mg/m3) absorption coefficient (mm−1) F(000) crystal size (mm) Θ range for data collection (deg) limiting indices reflections collected/unique completeness to θ = 27.48 absorption correction max and min transmission refinement method data/restraints/parameters goodness-of-fit on F2 final R indices [I > 2σ(I)] R indices (all data) largest diff peak and hole

1

2

3

C48H174Al9B45N24O102 3449.37 293(2) 0.71073 monoclinic, P21 9.2128(10) 38.528(5) 19.601(2) 90 91.952(2) 90 6953.5(14) 2, 1.647 0.196 3576 0.256 × 0.213 × 0.197 2.079−25.681

C16H58Al3B15N12O30 1141.83 293(2) 0.71073 orthorhombic, Pna21 16.4465(3) 21.8990(4) 13.3062(3) 90 90 90 4792.39(16) 4, 1.583 0.185 2367 0.164 × 0.148 × 0.123 2.912−29.480

C5H18B5GaN2O11 405.98 293(2) 0.71073 orthorhombic, Pna21 14.2094(6) 7.0929(3) 13.8368(7) 90 90 90 1394.55(11) 4, 1.934 2.036 824 0.217 × 0.206 × 0.189 2.867−25.676

−11 ≤ h ≤ 11, −50 ≤ k ≤ 50, −25 ≤ l ≤ 25 48209/24545 (Rint = 0.0331) 98.8% semiempirical from equivalents 1.0000 and 0.6262 full-matrix least-squares on F2 24545/176/2028 1.033 R1 = 0.0860, wR2 = 0.2272 R1 = 0.0898, wR2 = 0.2333 1.849 and −0.935 e·A−3



Figure 1. (a) Asymmetric unit of 1. (b) The polyhedral representation and (c) the topology of the framework of 1 along the a-axis. The arrows indicate the opposite arrangement of the channels with 8-, 11-, and 12 MR. Color code: Al (pink), B (green/yellow), O (red), C (white), N (blue), H (gray); AlO4 (pink), BO4 (yellow), BO3 (green). Synthesis. (H3APEA)6[AlB5O10]9·12H2O (1). A mixture of Al(iPrO)3 (0.204 g, 1 mmol), H3BO3 (0.372 g, 6 mmol), and a mixed solvent of N,N′-bis(3-aminopropyl)ethylenediamine (APEA, 1 mL), H2O (0.5 mL), and pyridine (3.5 mL) was stirred for an hour, following heated at 180 °C in a sealed 30 mL Teflon-lined bomb for 7 days. The mixture was then cooled to RT naturally, and the product was washed by distilled water and dried in air. The block colorless crystals of 1 were obtained in a yield of 65% based in Al(i-PrO)3. Anal. Calcd. for 1: C, 16.71; N, 9.75; H, 5.08; found: C, 16.70; N, 9.85; H, 4.75. (HDETA)2(H2DETA)2[AlB5O10]3 (2). Compound 2 was obtained by procedure similar to that for 1, except that the APEA (1 mL) was replaced by diethylenetriamine (DETA, 3 mL), and the amount of pyridine was reduced to 0.5 mL. The block colorless crystals of 2 were

selected as a standard (100% reflectance). The absorption data were obtained from reflectance spectra using the Kubelka−Munk function: F(R) = (1 − R)2/2R, where F(R) is the absorption coefficient and R is the reflectance.9 The Fourier transform infrared (FTIR) spectra (KBr pellets) were obtained on an ABB Bomen MB 102 spectrometer in the range of 4000−400 cm−1. Powder X-ray diffraction (PXRD) patterns were measured in the angular range of 2θ = 5−50° on a Rigaku DMAX 2500 diffractometer using Cu Kα radiation (λ = 1.5418 Å). Thermogravimetric (TG) analysis was done using a Mettler TGA/SDTA 851e analyzer (heating rate: 10 °C min−1) under air atmosphere in the temperature range of 30−1000 °C. The fundamental wavelength was 1064 nm and was generated by a Qswitched Nd:YAG laser. The second harmonic generation (SHG) wavelength was 532 nm. Sieved KDP powder was in the range of 25− 45, 45−62, 62−75, 75−109, 109−150, 150−212, and 212−300 mm. B


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Inorganic Chemistry

Figure 2. (a) The asymmetric unit of 2. (b) Polyhedral representation of the framework of 2 in the c-axis, and the side view of the zigzag channels with 11-MR [Al3B8] windows (red). (c) Topology of the framework of 2. (d) Polyhedral representation of the framework of 2 in the b-axis, and the side view of the channels with 11-MR [Al3B8] windows (red and blue highlighted areas represent a pair of channel enantiomers, and the dark and pale colors represent the opposite orientations of the same enantiomer). (e) Polyhedral representation of the framework of 2 in [310] direction, and the side view of the channels with 11-MR [Al3B8] windows. Color code: Al (pink), B (green/yellow), O (red), C (white), N (blue), H (gray); AlO4 (pink), BO4 (yellow), BO3 (green).

O−Al−O bond angles are in the range of 95.3(5)−123.8(6)o. Six (Al1, Al2, Al3, Al4, Al6, and Al9) of the nine Al atoms are connected to 11 others through four B5O10 clusters, simply named 11-connected Al, whereas six B5O10 clusters in the asymmetric unit is connected to 11 others through four Al atoms. Other Al atoms (Al5, Al7, and Al8) are 12-connected. That means each of them links 12 other Al atoms through four surrounding B5O10 clusters and also three B5O10 clusters links to other 12 B5O10 clusters through four Al atoms. The 11- and 12-connected Al atoms are commonly observed in ABOs,6l,7a but the coexistence of two types of Al atoms in one framework has never been reported. The interconnection of equivalent Al atoms and B5O10 clusters leads to a three-dimensional (3D) [AlB5O10]n2n− framework, which possesses channels with 8-, 11-, and 12membered ring (MR) windows. All of these channels, extended along the [100] direction, are arranged in the ···8− 11−12−8−11−12··· or ···12−11−8−12−11−8··· order in the c-direction (Figure 1b). Because of the presence of a 21 screw axis along the b-axis, every three rows of the above-mentioned parallel channel arrangements can be viewed as a repeating layered unit. Each layered unit is connected with two neighboring units in an antiparallel fashion (i.e., the red- and light-red-highlighted areas in Figure 1b). Consequently, from the view along the a-axis, the corresponding channels with a certain nMR-Q (n = 8, 11, 12; Q = I, II, III) window exhibit the same configuration but opposite orientation (Q and Q′) in each pair of neighboring layered units. In this case, the framework can be depicted as the stacking of the channel arrangement nets in the ABCA′B′C′ mode along the b-axis and ABCABC sequences along the c-axis (Figure S1). Therefore, there are in total nine types of channels together in one repeating layered unit in the framework.

obtained in a yield of 76% based in Al(i-PrO)3. Anal. Calcd. for 2: C, 16.83; N, 14.72; H, 5.12; found: C, 16.98; N, 14.98; H, 4.99. (H2EDAP)[GaB5O10]·H2O (3). The block colorless crystals of 3 were made by a similar method used in the synthesis of 1 except that Al(iPrO)3 (0.204 g, 1 mmol) and APEA (1 mL) were replaced by Ga(iPrO)3 (0.123 g, 0.5 mmol) and N-ethyldiaminopropane (EDAP, 0.5 mL). 3 was obtained in a yield of 29% based in Ga(i-PrO)3. Anal. Calcd. for 3: C, 14.79 N, 6.90; H, 4.47; found: C, 14.72; N, 7.07; H, 4.79. Single-Crystal Structure Determination. The intensity data of 1 were collected on a Saturn724 CCD with graphite-monochromated Mo Kα radiation (λ = 0.71073 Å), and those of 2 and 3 were collected on a SuperNova, Atlas diffractometer equipped with mirrormonochromated Mo Kα radiation at RT. The structures were solved by direct methods and refined by full-matrix least-squares on F2 with the SHELXTL-2014 package.10,11 All the non-H atoms were refined anisotropically. The H atoms of organic amines and water molecules were geometrically generated and refined using a riding model, and the protonated N atoms were determined by the formation of hydrogen bonds. In 1, four water molecules in the lattice could not be found through single-crystal structure determination and were determined by elemental analysis and TG analysis. The crystal data and structure refinement details are listed in Table 1.

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RESULTS AND DISCUSSION Structure Description. (H3APEA)6[AlB5O10]9·12H2O (1). The crystal structure analysis shows that 1 crystallizes in the monoclinic space group P21. The asymmetric unit contains nine tetrahedrally coordinated Al atoms, nine pentanuclear B5O10 clusters, six protonated amine ions, and eight lattice water molecules (Figure 1a). For the B5O10 cluster, the central B atom adopts tetrahedral coordination geometry and is connected with a pair of dimeric B2O5 groups, where the B atoms adopt triangle planar geometry. This configuration leads to two B3O3 rings nearly perpendicular to each other. The Al− O bond lengths range from 1.617(12) to 1.863(12) Å, and the C


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Inorganic Chemistry

Figure 3. (a) The asymmetric unit of 3. (b) Polyhedral representation of the framework of 3 and three pairs of 8-MR helical channels in [001] direction. Polyhedral representation of the framework of 3 in (c) [100] and (d) [010] directions, and the corresponding side views of the channels with 11-MR [Ga3B8] window (red and blue highlighted areas represent a pair of channel enantiomers, and the dark and pale colors represent the opposite orientations of the same enantiomer). Color code: Ga (purple), B (green/yellow), O (red), C (white), N (blue), H (gray); GaO4 (purple), BO4 (yellow), BO3 (green).

for type III), in accordance with the 21 symmetric operation in the Pna21 space group. If the AlO4 tetrahedra and B5O10 clusters are considered as 4-connected nodes, the framework of 2 possesses a lon net and its Schläfli symbol is {66} (Figure 2c). Furthermore, the natural tiling12 envisaged on the framework indicates a signature of [63]+[65] (Figure S2).The protonated amine cations located in the middle of channels interact with the inorganic wall by hydrogen bonds (Table S1). According to the PLATON analysis, there is a solvent-accessible volume as large as 58.5% in the structure. (H2EDAP)[GaB5O10]·H2O (3). Compound 3 belongs to orthorhombic space group Pna21 and the asymmetric unit has one Ga atom, one unique B5O10 unit, one (H2EDAP)2+ cation, and one H2O molecule (Figure 3a). Four O atoms bond the Ga center to form GaO4 tetrahedron (the Ga−O bond lengths: 1.805(5)−1.834(3) Å; the O−Ga−O bond angles: 105.6(2)−111.5(2)°). In compound 3, GaO4 interconnects with 12 adjacent ones through B5O10 clusters in a distinct way from that of 2, forming a different acentric structure (Figure 3b). This framework contains intersected channels parallel to a-/b-/c-axes. Along the c-axis, B5O10 clusters are alternatingly linked by equivalent GaO4 tetrahedra to form three types of left-handed helices (IL, IIL, and IIIL) and their right-handed enantiomers (IR, IIR, and IIIR). All of them have a pitch of 13.837 Å. In comparison, the channels along the a-/b-axes exhibit larger 11-MR [Ga3B8] windows; nevertheless, they differ from each other in the pore shape and dimension. On the one hand, the channels running along the aaxis display round cross sections of ca. 7.09 × 6.54 Å2. The adjacent arrays of channels arranged parallel to the b-axis adopt the same architecture but opposite orientations (pale and dark red in Figure 3c), in accordance with the 21 symmetric operation in the space group Pna21. On the other hand, the channels running along the b-axis display an oblate shape, with

Considering the AlO4 groups and B5O10 clusters as 4connected nodes, the framework of 1 has a new 3-nodal topology with a Schlä fl i symbol of {4.6 5 } 2 {6 6 } and stoichiometry (4-c)(4-c)(4-c) (Figure 1c). The protonated APEA are trapped in the channels, interacting with the framework by H-bonds (Table S1). The solvent-accessible volume of the framework is about 56.5% via the PLATON analysis, suggesting the existence of large voids in the structure. (HDETA)2(H2DETA)2[AlB5O10]3 (2). 2 crystallizes in the acentric orthorhombic space group Pna21. There are three Al atoms, three B5O10 groups, two [H2DETA]2+ cations, and two [HDETA]+ cations in the asymmetric unit (Figure 2a). All the Al centers are coordinated by 4 O atoms, adopting the tetrahedral coordination geometry (Al−O bond lengths: 1.699(3)−1.753(3) Å; O−Al−O bond angles: 106.46(2)− 111.86(2)o). Each AlO4 unit is linked to other 12 same ones through four B5O10 clusters, forming a 3-D [AlB5O10]n2n− framework with intersecting channels of 11-MR [Al3B8] windows. These channels can be divided into three categories (I, II, and III) according to their extension along the [001], [010], and [310] directions (Figures 2b, d, and e). (a) The channels running along the c-axis (type I) exhibit the same zigzag architecture (Figure 2b right) but with different distortion because of the pseudo mirror symmetry in their absolute configuration. In addition, the 21 screw axes and glide planes endow these channels identical orientations in the whole crystal lattice. (b) The channels extended along the [010]/[310] (type II/III) directions display straight architectures (Figures 2d right and e right). The aligned packing of [Al3B8] windows in these two types of channels results in larger cross sections (9.10 × 6.90 Å for type II and 9.18 × 6.67 Å for type III) compared to that of type I (7.70 × 7.65 Å). The channels in adjacent rows adopt the same architecture but opposite orientations (see Figures 2d and e, pale and dark blue for type II and pale and dark purple D


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Inorganic Chemistry the cross sections of ca. 10.86 × 6.30 Å. In analogy, the 21 symmetric operation results in an opposite orientations of the channels in neighboring rows (pale and dark red/blue in Figure 3d). Furthermore, the channels in the same array parallel to the a-axis exhibit an alternating arrangement of the enantiomeric architectures (shown as dark red and blue or pale red and blue in Figure 3d), owing to the presence of the glide plane A perpendicular to the b-axis. The organic amines are sited in the intersecting channels and interact with the GBO framework via H-bonds (Table S1). If both the GaO4tetrahedra and B5O10 clusters are considered as 4-connected nodes, the topology of 3 turns out to be a dia net with total Schläfli symbol of {66}. The framework can also be viewed in terms of natural tiling with signature [64] (Figure S3). The results of the PLATON analysis show that the framework exists in a solvent-accessible volume of ca 51.4%. Comparison of [MB5O10]n2n− Frameworks. Compounds 1, 2, and 3 consist of [MB5O10]n2n− (M = Al, Ga) frameworks that are constructed of MO4 tetrahedra and B5O10 clusters. All of them are the assemblies of similar {MB5O10} layers with 11MR windows, which can be simplified to graphene-like layers when MO4 and B5O10 are regarded as 3-connected nodes. The adherence of these layers is achieved through the corner-shared O bridges between MO4 and B5O10 groups, respectively, from two adjacent layers. That is to say, there is no MO4-MO4 or B5O10-B5O10 linkage in all the three types of frameworks. In this context, the architectural difference between 1, 2, and 3 lies in the interlamellar linkage modes, which can be divided into three categories. The mode I (Figure 4) stands for the

instance, frameworks of 2 and 3 feature the interlinkage of adjacent layers in mode I and III, respectively. In contrast, two types of linkage modes (mode I and mode II) were observed in the construction of the framework of 1. Adjacent {MB5O10} layers stack along the b-axis and connected with each other in a mode sequence of −II−I−II−II−I−II−. Owing to many MBO frameworks that are built from {MB5O10} layers with various linkage modes, we compared the compound 3 with four reported organic amine-templated MBOs, [(C5H16N2)(AlB5O10)]·2H2O (3a),7b [C5N2H16]AlB5O10 (3b),13 [H2dap][(CH3)2NH]AlB5O10 (3c),13 and [H2TETA]AlB5O10 (3d).14 The linkage fashion of 3a, 3b, and 3 belongs to the above-mentioned mode III, and their frameworks are all dia net with total Schläfli symbol of {66}. The frameworks in 3a, 3b, and 3 contain 11-MR channels and 8-MR helical channels, but the windows vary in shape and size. The linkage modes of the layers in 3c and 3d are similar to mode II with a similar edge−edge fashion but different linkage node position. Therefore, the frameworks of 3c and 3d have crb and sra topology, respectively (Figure S4). ABO/GBOs Framework Containing Organic Amines. Here, the organic amines are introduced into ABO/GBO materials under mild solvothermal conditions, which have been proven to be useful for enhancing the structural variety and have led to rapid progress in the last two decades. On the one hand, organic amines, varying in size and shape, can enter the structures as SDAs, space-filling and charge-balancing agents, interacting with the framework through electrostatic interactions and H-bonds. On the other hand, B5O10 cluster is structurally complex and possesses sufficient oxygen atoms to build up versatile hydrogen bond networks. These two aspects contribute to a complicated relationship between ABO/GBO framework and organic amine templates. This encourages us to explore the roles of amines in the formation of the crystalline products in this paper. The organic amines in 1−3 contain long carbon chains and multiple N donors. Taking 1 as an example, the APEA, consisting of two 3-aminopropyl groups, respectively, connected to two N atoms of the central ethylenediamino group, possess a large dimension of ca. 11 Å by measuring the interatomic distance between two ending N atoms in 1. Undoubtedly, the relatively larger size and more flexible configuration of such long chain-like organic amines will contribute some special features to the overall structures of the inorganic frameworks. (a) The amines with longer alkyl groups can adopt flexible orientation in the voids of the inorganic framework because of the free rotation of the C−C or C−N bonds. On the one hand, this can be revealed by the presence of six and four amine SDAs with different conformations in the asymmetric unit of compounds 1 and 2, respectively. On the other hand, particular SDA with conformational flexibility is a good match with different anionic frameworks. For example, compounds [NH 3 (CH 2 ) 2 NH(CH 2 ) 2 NH 3 ] 2 [Al 2 B 10 O 20 ]· 4H2O7f and 2 are both templated by diethylenetriamine, which nevertheless adopted different conformations. Correspondingly, their frameworks display critical structural distinctions and exhibit to be dia and lon topologies, respectively. (b) The −NHx group and carbon skeleton as hydrophilic and hydrophobic groups endows the surfactantlike behavior to organic amines. The −NHx groups are inclined to locate in the most reasonable sites to form N−H···O hydrogen bonds with the inorganic moieties, consequently affecting the overall structure of the inorganic host. For

Figure 4. Comparison of compounds 1, 2, and 3.

interconnection of the edge and the diagonal of the hexagons from two adjacent layers and can be abbreviated as an edge− diagonal linking fashion. In comparison, the mode II features a parallel linkage of two edges of the hexagons from two adjacent layers, leading to an edge−edge fashion. While in mode III, one node from each hexagon links to the parallel node with an anticlockwise rotation of 60° of the neighboring layer. The versatile linkage modes between layers, together with different distortions of the layers, contribute to the complicated architectural distinctions among the three frameworks. For E


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Inorganic Chemistry

In the FTIR spectra (Figure S5), the peaks at about 1398, 1420, and 1377 cm−1 indicate the presences of BO3 triangles, while the bands at 1066, 1071, and 1049 cm−1 are the characteristic signals of B−O vibration of BO4 groups. The broad bands at 3470−2851 cm−1 can be assigned as the stretching vibrations of the N−H and C−H bonds. The bending vibrations of N−H/C−H are represented by the bands at 1634−1540 cm−1 in the spectra. UV−vis diffuse-reflectance spectra of 1−3 indicate that they are all wide band gap semiconductors, and the optical band gaps are respectively 5.59, 5.58, and 5.07 eV (Figure 6 right), which are comparable to other documented ABO/GBOs.6a NLO Determination. Because compounds 1−3 are the acentric structures, their SHG measurements on the powder samples were carried out at RT by the Kurtz−Perry method.15 The intensity of the green light (λ = 532 nm) generated by the crystalline powders of 1, 2, and 3 exhibited SHG responses approximately 0.3, 1.5, and 0.5 times that of KDP (KH2PO4) powder, respectively (Figure 7). The increasing tendency of

example, the conformationally varied amines in 1, 2, and 3 match well with their unique frameworks with specific channel environments, leading to complicated hydrogen bond networks (Figure 5).

Figure 5. Hydrogen bonds in 1−3.

PXRD, FTIR, and UV−vis Characterizations. The PXRD patterns of 1−3 are provided in Figure 6 left, in which the 2θ peaks match well with those of the simulated patterns from the single-crystal XRD data, suggesting all the samples are pure. Because of the preferred orientations of the polycrystalline samples, the intensities of some peaks do not fit well with the simulated ones.

Figure 7. Oscilloscope traces of SHG signals for the powder of KDP and compounds 1−3 in the same particle size of 109−150 μm (top). Phase matching curve, that is, particle size versus SHG intensity data for 2 (bottom).

the SHG efficiency toward the particle size efficiency indicates a typical type I phase-match for compound 2. On the basis of the anionic-group theory,16 the BO3 units, with different number density and overall arrangement, influence the SHG behavior of borate NLO materials. As described in the Structure Description section, although compounds 1−3 contain the same BO3 unit, the arrangement of BO3 units is not totally in the same orientation. Therefore, they display different SHG responses.

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CONCLUSIONS In summary, three ABO/GBOs were made under solvothermal conditions by using long chain-like organic amines as SDAs. Compounds 1−3 feature the [MB5O10]n2n− frameworks that

Figure 6. PXRD (left) and UV−vis spectra (right) of 1−3. F


Article

Inorganic Chemistry

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are all built from MO4 (M = Al or Ga) tetrahedra and B5O10 clusters; nevertheless, they exhibit different structures, intersected channels, as well as topologies. They all crystallize in polar space groups and show efficient SHG. This study also illustrates the effluence of the organic amines on the ABO/ GBO frameworks, which offers the potential to design metal borates and explore their NLO properties. Further work is currently underway, and the respective results will be reported elsewhere in due course.

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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.8b01925. Additional structure pictures, IR and TG results, hydrogen bond table (PDF) Accession Codes

CCDC 1553422−1553424 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, 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-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 (Grants 21501133, 21571060, and 91122028), the NSFC for Distinguished Young scholars (Grant 20725101) and the Doctoral Program Foundation of Tianjin Normal University (Grant 52XB1409).

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REFERENCES

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Galloborate Frameworks Templated by Organic

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