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A porous-layered aluminoborate built by mixed oxoboron clusters and AlO4 tetrahedra

Juan CHEN ,  Guoyu YANG

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Citation:  Juan CHEN, Guoyu YANG. A porous-layered aluminoborate built by mixed oxoboron clusters and AlO4 tetrahedra[J]. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 193-200. doi: 10.11862/CJIC.20240341 shu

一个基于混合硼氧簇及AlO4四面体构建的孔层结构硼酸铝

  • .

    北京理工大学化学与化工学院, 原子分子簇科学教育部重点实验室, 北京 102488

    • 通讯作者: 杨国昱, ygy@bit.edu.cn
  • 基金项目:

    国家自然科学基金 21831001

    国家自然科学基金 21971011

摘要: 以碱金属阳离子为结构导向剂, 在溶剂热条件下合成了一个基于混合硼氧团簇单元及AlO4四面体构建的硼酸铝: Na2.5Rb[Al{B5O10}{B3O5}]·0.5NO3·H2O (1)。结构中, [B5O10]5-和[B3O7]5-两种单元交替连接形成一维[B8O15]n6n-链, 链与链之间通过AlO4四面体连接形成具有七元环和十元环窗口的二维层, 相邻取向相反的2个单层进一步通过B—O—Al键构成具有6种类型孔道的孔层结构。通过单晶X射线衍射、粉末X射线衍射、红外光谱、紫外可见漫反射光谱以及热重分析对该化合物进行了结构表征和性能研究。紫外可见漫反射光谱分析表明, 化合物1的紫外吸收截止边为201 nm。

English

  • 0.   Introduction

    Short-wavelength optical crystals play a crucial role in ultraviolet (UV) and deep ultraviolet (DUV) laser technologies, serving as indispensable components in applications such as laser-driven interference lithography, precise micro-machining, as well as spectroscopy[1-4]. For instance, UV nonlinear optical (NLO) crystals can quadruple the frequency of the Nd∶YAG (Nd∶Y3Al5O12) laser output to generate 266 nm light, and deep UV birefringent crystals can modulate the polarization of light through their birefringent property. Borates have emerged as important candidate materials for UV/DUV optical applications in recent years due to their excellent optical properties and diverse structural types. Extensive research and exploration have focused on developing a range of borate crystals with versatile properties, including β-BaB2O4 (BBO)[5], LiB3O5 (LBO)[6], CsB3O5 (CBO)[7], KBe2BO3F2 (KBBF)[8] and so on. Structurally, B atoms can interact with O atoms to form triangular BO3 and tetrahedral BO4 units, which are interconnected through shared corners/edges, giving rise to various fundamental building blocks (FBBs). The FBBs can further polymerize into frameworks of different dimensions, including isolated clusters, 1D chains, 2D layers, and 3D networks[9-13].

    Recently, advancements in the incorporation of heteroatoms into borate frameworks have led to the development of several novel systems, including B-O-Zn, B-O-Ge, and B-O-V[14-18]. Al, positioned in the same main group as B, offers distinct advantages for synthesizing new aluminoborates (ABOs). Specifically, Al exhibits multiple coordination modes such as tetrahedral AlO4, trigonal bipyramidal or square‑pyramidal AlO5, and octahedral AlO6[19-22]. These AlOn polyhedra can integrate with B-O clusters, thereby enhancing the dimensionality and structural complexity of the frameworks through covalent Al—O bonds[23-24]. Since 2009, our group has concentrated on the synthesis of open-framework ABOs using aluminum isopropoxide (Al(iPrO)3) under hydrothermal and solvothermal conditions[25]. We choose to use Al(iPrO)3 instead of traditional sources like Al2O3, AlCl3, or Al(NO3)3 because the chiral Al center can gradually transform from a three‑coordinate Al(iPrO)3 to a four-coordinate AlO4 group through hydrolysis during the crystallization process[26]. The synergistic effect between chiral AlO4 groups and acentric B-O clusters formed in situ self-polymerization has been shown to significantly facilitate the formation of acentric ABOs[27-30]. For example, The acentric structure of [Zn(dap)2][AlB5O10] (dap=1, 3-diaminopropane) is distinguished by its 3D inorganic aluminoborate framework and 2D metal‑organic coordination network[28]. BIT-1 exhibits a CAN-type chiral ABO with giant 24‑MR (membered ring) channels[29]. Na1.5Cs0.5[Al{BO3}{B9O15(OH)3}1/3] demonstrates a new layered structure containing the largest oxoboron cluster [B9O15(OH)3]6- among acentric borates[30]. This method has achieved significant advancements in systems involving inorganic cations, organic amines, and metal complexes, greatly expanding the structural diversity of aluminoborates and leading to the synthesis of a series of novel compounds with optical properties[31].

    The 3D porous layered structure represents a new type of open framework. The porous layer was first found in a silicate (AMH-3) and followed by a borogermanate K4[B8Ge2O17(OH)2][32-33]. After that, Yang's group further developed this system in borates and synthesized several 3D porous-layered structures, including Ba3M2[B3O6(OH)]2[B4O7(OH)2] (M=Al/Ga)[34], Ba[MB4O8(OH)]·H2O (M=Al/Ga)[35], NaK1.5[B{B5O9(OH)}{B5O8(OH)2}1/2][36], and [H3O]K3.52Na3.48{Al2[B7O13(OH)][B5O10][B3O5]}[CO3][37]. These structures generally have mixed clusters, diverse configurations, and abundant channels, which is uncommon in borates. As a continuation of our work, a new aluminoborate, Na2.5Rb[Al{B5O10}{B3O5}]·0.5NO3·H2O (1), has been synthesized under hydrothermal conditions. 1 exhibits a 3D porous‑layered structure built by [B5O10]5- and [B3O7]5- clusters and AlO4 units. The strict alternation of mixed oxoboron clusters and AlO4 tetrahedra leads to the open framework containing six types of channels.

    1.   Experimental

    1.1   Materials and methods

    The raw materials include H3BO3 (Aladdin, 99.5%), NaOH (Aladdin, 98%), Rb2CO3 (Aladdin, 99.8%), Ca(NO3)2 (Aladdin, 99.5%) and Al(iPrO)3 (Macklin, 99.8%), which were purchased from commercially available sources and used without purification. Infrared spectrum (IR) was recorded on a Nicolet iS10 FTIR instrument (KBr pellets) in the 400-4 000 cm-1 wavenumber range. UV-Vis spectrum was obtained on a Shimadzu UV-3600 spectrometer, fitted with BaSO4 as the standard material in the wavelength region of 190-800 nm. Powder X-ray diffraction (PXRD) data was collected on a Bruker D8 Advance X-ray diffractometer using a voltage of 40 kV and a current of 40 mA in the range of 2θ=5°-50° with a step size of 0.02° at room temperature (Cu Kα radiation, λ=0.154 056 nm). Thermogravimetric analysis (TGA) was determined by a Mettler Toledo TGA/DSC 1100 analyzer from 25 to 1 000 ℃ with a heating rate of 10 ℃·min-1 under an air atmosphere.

    1.2   Synthesis of 1

    A mixture of H3BO3 (0.243 g, 4.0 mmol), NaOH (0.04 g, 1.0 mmol), Rb2CO3 (0.106 g, 0.46 mmol), Ca(NO3)2 (0.041 g, 0.25 mmol), and Al(iPrO)3 (0.102 g, 0.5 mmol) was added into a 25 mL Teflon‑lined stainless-steel autoclave. Then 2 mL of H2O and 2 mL of EtOH were added into the autoclave and stirred for 1 h. The autoclave was sealed and heated at 210 ℃ for 6 d. After cooling down to room temperature and filtered with distilled water, colorless block crystals were obtained. Yield: 70% based on NaOH.

    1.3   Single crystal structure determination

    Single crystal X-ray diffraction data for 1 were collected on a GeminiA Ultra instrument, using graphite monochromatic Mo Kα radiation (λ=0.071 073 nm) at 293 K. The structure was solved by the intrinsic phasing method and refined by full-matrix least-squares methods on F 2 using the SHELXT program package embedded in Olex2 software[38-39]. Anisotropic displacement parameters were refined for all atomic sites except hydrogen atoms. The hydrogen atoms were geometrically placed and refined by the riding model. The ADDSYM algorithm in the PLATON program was used to verify the structures, and no higher symmetries were found. The crystallographic data and structure refinement parameters for 1 are listed in Table 1.

    Table 1

    Table 1.  Crystal data and structure refinements for 1
    下载: 导出CSV
    Parameter 1 Parameter 1
    Empirical formula Na2.5Rb[Al{B5O10}{B3O5}]·0.5NO3·H2O Z 2
    Formula weight 545.43 Dc / (g·cm-3) 2.412
    Crystal system Triclinic μ/mm-1 3.529
    Space group P1 F(000) 526
    a/nm 0.704 98(5) Reflection collected 8 926
    b/nm 1.031 02(9) Independent reflection 3 679
    c/nm 1.092 17(8) Rint 0.042 2
    α/(°) 103.525(7) Data, restraint, number of parameters 3 679, 46, 295
    β/(°) 98.706(6) Goodness-of-fit on F 2 1.069
    γ/(°) 97.688(6) Final R indices [I > 2σ(I)]a R1=0.043 7, wR2=0.091 1
    V/nm3 0.751 02(10) R indices (all data)b R1=0.064 0, wR2=0.101 7
    a R1=∑||Fo|-|Fc||/∑|Fo|; b wR2=[∑w(Fo2-Fc2)2/∑w(Fo2)2]1/2.

    2.   Results and discussion

    2.1   Description of crystal structure

    Single-crystal XRD analysis shows that 1 crystallizes in the triclinic space group P1. Its asymmetric anionic unit (Fig. 1a) contains [B8O15]6- cluster built from [B5O10]5- and [B3O5]- clusters, one unique Al atom, 0.5 NO3- group, and one water molecule. According to the classification of oxoboron clusters proposed by Heller, Christ, and Clark[40], [B5O10]5- and [B3O7]5- clusters can be written in the shorthand notation of [5:(4Δ+1T)] and [3:(2Δ+1T)], respectively. Each [B5O10]5- cluster links to two [B3O7]5- rings and two AlO4 tetrahedra (Fig. 1b). Each [B3O7]5- cluster binds to two [B5O10]5- clusters and two AlO4 groups (Fig. 1c), and each AlO4 tetrahedron connects two [B5O10]5- clusters and two [B3O7]5- clusters (Fig. 1d). The B—O bond distances and the O—B—O bond angles are in the ranges of 0.133 2-0.148 8 nm and 107.1°-124.1°, respectively. The Al—O bond lengths and O—Al—O bond angles are in the ranges of 0.171 6-0.176 4 nm and 105.5°-112.2°, respectively. The N—O bond lengths are in the range of 0.120 2-0.122 5 nm, shorter than the B—O bond lengths, which are in agreement with those previously reported[41-43].

    Figure 1

    Figure 1.  (a) Asymmetric unit of 1; Coordination environments of (b) [B5O10]5- cluster, (c) [B3O7]5- cluster, and (d) AlO4 tetrahedron

    Color codes: green, [B5O10]5- cluster; yellow, [B3O7]5- cluster; pink, AlO4 tetrahedron; Symmetric codes: #1: 2-x, 2-y, 1-z; #2: 1+x, 1+y, z; #3: x, 1+y, z; #4: -1+x, y, z.

    下载: 全尺寸图片 幻灯片

    In 1, the [B5O10]5-and [B3O7]5- clusters link together to form a 1D [B8O15]n6n- chain along the a-axis. The 1D chains are joined by AlO4 tetrahedra to produce 2D monolayers with 8- and 10-MR windows in the ac plane (Fig. 2a). The 8-MR windows are built by one [B5O10]5- cluster, two [B3O7]5- clusters and one AlO4 tetrahedron, and the 10-MR windows are constructed by two [B5O10]5- clusters, two [B3O7]5- clusters, and two AlO4 tetrahedra. Furthermore, the adjacent monolayers with opposite orientations are connected by B—O—Al bonds to form a 3D framework stacked in the -AAA- sequence along the c‑axis (Fig. 2b), including channels A and B (Fig. 3a).

    Figure 2

    Figure 2.  (a) View of a 2D monolayer with 8- and 10-MR windows; (b) Porous layer stacked in -AAA- mode

    Color codes: green, [B5O10]5- cluster; yellow, [B3O7]5- cluster; pink, AlO4 tetrahedron.

    下载: 全尺寸图片 幻灯片

    Figure 3

    Figure 3.  (a) Two types of channels along the a-axis; (b) View of window Ⅰ; (c) View of window Ⅱ; (d-g) Four types of channels along different directions; (h) Six types of intercommunicated channel networks

    Symmetric codes: #1: 1+x, y, z; #2: 1+x, -1+y, z; #3: 3-x, 1-y, 1-z; #4: 2-x, 1-y, 1-z; #5: 2-x, 2-y, 1-z.

    下载: 全尺寸图片 幻灯片

    Interestingly, there exist six types of channels. Along the a-axis, channel A with a pore diameter of 1.02 nm×0.50 nm is built by 10-MR windows (window Ⅰ) while channel B with a pore diameter of 0.86 nm×0.48 nm is made of 8-MR windows (window Ⅱ). Window Ⅰ is formed by two [B5O10]5- clusters, two [B3O7]5- clusters, and two AlO4 groups, including AlO4-B8O3-B6O4-B2O3-B1O3-AlO4-B8O3-B6O4-B2O3-B1O3 linkages (Fig. 3b). Window Ⅱ is constructed by two [B5O10]5- clusters and two AlO4 groups in the AlO4-B1O3-B3O4-B4O3-AlO4-B1O3-B3O4-B4O3 linkages (Fig. 3c). Along the b-axis, channel C measures 0.90 nm×0.52 nm and is composed of the alternation of window Ⅰ and 12-MR windows in which the 12-MR window contains two repeating AlO4-B1O3-B3O4-B5O3-B6O4-B7O3 linkages (Fig. 3d and S1, Supporting information). Channel D is limited by the alternation of window Ⅰ and Ⅱ along [110] direction, resulting in a dimension of 0.50 nm×0.49 nm (Fig. 3e and S1). Channels E and F appeared along [110] direction with the free dimensions of 1.02 nm×0.50 nm and 0.81 nm×0.46 nm, respectively. Channel E is formed by window Ⅰ while channel F is formed by 11-MR windows with the connectivity of AlO4-B1O3-B2O3-B6O4-B7O3-AlO4-B1O3-B3O4-B5O3-B6O4-B8O3 (Fig. 3f and 3g). The six types of channels intercommunicate to form a complicated channel system (Fig. 3h).

    As for metal atoms, Na1, Na2, and Na3 atoms link with 7, 7, and 8 O atoms with Na—O bond lengths of 0.233 7-0.298 7 nm. Rb atoms link with 8 O atoms with Rb—O bond lengths of 0.288 0-0.325 1 nm. Na2 atom is located in the 10-MR channel A while the Na3 atom is in the 8-MR channel B. In addition, Na1 and Rb atoms reside in the interlayer, and NO3- groups exist in 8-MR channels B (Fig.S2).

    Several kinds of octaborate clusters constructed from {B5} and {B3} sub-cluster have been reported (Table 2), including [B8O12(OH)4]4- [44-45], [B8O14(OH)4]8- [46], [B8O12(OH)2]2- [47], and [B8O16]8- [48-50]. Flexible assembly of B‑O clusters significantly affects the overall structure. First, different arrangements of hydroxyl groups lead to different structures. For example, [NH3CH2CH(CH3)NH3][B8O11(OH)4]·H2O[44] and [Zn(en)2{B8O11(OH)4}] (en=ethylenediamine)[45] contain [B8O12(OH)4]4- clusters, but possess different 1D chains (Fig.S3). The former is formed by the expansion of the [B3O6(OH)]4- cluster in a 2-connected manner, and the [B5O7(OH)3]2- has only a decorative role. The latter, however, is made up of the alternation of [B3O5(OH)2]3- and [B5O8(OH)2]3- clusters. Second, different numbers of BO3/BO4 groups and hydroxyl groups result in different structures (Fig.S4). The FBB of Li4Ca2[B8O12(OH)4]2·3H2O[46] is [B8O14(OH)4]8-, which is made of [B5O10(OH)]6- cluster and [B3O5(OH)3]4- ring, in which [B5O10(OH)]6- clusters are connected to form 1D chains, and [B3O5(OH)3]4- units act as bridges to connect adjacent chains to produce 2D layers. The [B8O12(OH)2]2- cluster in Na2(H2en)[B5O8(OH)]2[B3O4(OH)]2[47] extended to a 2D layer by the strict alternation of [B5O9(OH)]4- and [B3O6(OH)]4- clusters. Third, clusters with fewer hydroxyl groups tend to form high-dimensional structures. Borates containing [B8O16]8- cluster are 3D structures[48-50], such as LiNaB8O13, α‑LiKB8O13, and β‑LiKB8O13. Although the compounds contain the same anion clusters, they have different frameworks due to how the [B5O10]5- and [B3O7]5- clusters are connected (Fig.S5). Unlike the reported above, 1 contains a new 1D [B8O15]n6n- chain built from [B5O10]5-and [B3O7]5- clusters. Adjacent chains are joined by AlO4 tetrahedra to produce a 3D porous-layer structure.

    Table 2

    Table 2.  Known octaborates built from {B5} and {B3} sub-clusters
    下载: 导出CSV
    Formula Space group FBB Sub-cluster Dimension Ref.
    [NH3CH2CH(CH3)NH3][B8O11(OH)4]·H2O P21/c [B8O12(OH)4]4- [B3O6(OH)]4-+[B5O7(OH)3]2- 1D [44]
    [Zn(en)2{B8O11(OH)4}] P1 [B8O12(OH)4]4- [B3O5(OH)2]3-+[B5O8(OH)2]3- 1D [45]
    Li4Ca2[B8O12(OH)4]2·3H2O C2/c [B8O14(OH)4]8- [B3O5(OH)3]4-+[B5O10(OH)]6- 2D [46]
    Na2(H2en)[B5O8(OH)]2[B3O4(OH)]2 P21/c [B8O12(OH)2]2- [B3O6(OH)]4-+[B5O9(OH)]4- 2D [47]
    LiNaB8O13 C2/c [B8O16]8- [B3O7]5-+[B5O10]5- 3D [49]
    α-LiKB8O13 Pbca [B8O16]8- [B3O7]5-+[B5O10]5- 3D [49]
    β-LiKB8O13 P21/c [B8O16]8- [B3O7]5-+[B5O10]5- 3D [49]

    2.2   IR spectrum

    As shown in Fig. 4, the strong absorption around 3 456 cm-1 is attributed to the characteristic peaks of stretching vibrations of O—H bonds. Peaks at 1 641 cm-1 can be ascribed to the bending vibration of the O—H bonds. The overlap of the stretching vibration of the asymmetric BO3 units and triangular NO3- groups results in a strong absorption band of about 1 245-1 485 cm-1. The bands at 925-1 106 cm-1 originate from the asymmetric stretching vibration of BO4 tetrahedra.

    Figure 4

    Figure 4.  IR spectrum of 1
    下载: 全尺寸图片 幻灯片

    2.3   PXRD pattern

    The experimental PXRD pattern agreed with the calculated simulated pattern from the single crystal data, confirming the purities of compound 1 (Fig. 5). The slight difference between them may be due to the change in the preferred orientation of the powder sample during the acquisition of the experimental PXRD pattern.

    Figure 5

    Figure 5.  Experimental and simulated PXRD patterns of 1
    下载: 全尺寸图片 幻灯片

    2.4   TGA

    The thermal stability of 1 was examined from 25 to 1 000 ℃ with the heating rate of 10 ℃·min-1 (Fig. 6). There existed a two-step weight loss of 9.02% (Calcd. 8.98%) from 69 to 670 ℃. The 3.39% (Calcd. 3.30%) weight loss from 69 to 293 ℃ is attributed to the removal of one H2O molecule, while the subsequent 5.63% (Calcd. 5.68%) weight loss from 293 to 670 ℃ is due to the loss of 0.5 NO3- group.

    Figure 6

    Figure 6.  TGA curve of 1
    下载: 全尺寸图片 幻灯片

    2.5   UV-Vis diffuse reflectance spectrum

    The UV-Vis diffuse reflectance spectrum was obtained with a wavelength ranging from 190 to 800 nm. The absorption data was calculated using the Kubelka-Munk function: F(R)=(1-R)2/(2R)=α/S, where α is the absorption coefficient, S is the scattering coefficient, and R is the reflectance. As shown in Fig. 7, the UV cut-off edge for compound 1 was 201 nm, corresponding to the band gap (Eg) of 5.38 eV, respectively.

    Figure 7

    Figure 7.  UV-Vis diffuse reflectance spectrum of 1

    Inset: the corresponding bandgap.

    下载: 全尺寸图片 幻灯片

    3.   Conclusions

    In summary, a new borate Na2.5Rb[Al{B5O10}{B3O5}]·0.5NO3·H2O (1) was synthesized by hydrothermal reaction. Compound 1 contains [B8O16]8- cluster built from [B5O10]5- and [B3O7]5- groups and AlO4 tetrahedra. The strict alternation of [B5O10]5- and [B3O7]5- groups and AlO4 tetrahedra results in a 3D porous-layered structure with an abundant channel system. In addition, we discuss the reported and analyze the flexible assembly of their B-O units, which offers new perspectives for integrating inorganic compounds. UV-Vis reflectance spectrum reveals that compound 1 exhibits a short cutoff edge at 201 nm, corresponding to a bandgap of 5.38 eV, suggesting its potential for applications in the UV region.


    Supporting information is available at http://www.wjhxxb.cn
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  • Figure 1  (a) Asymmetric unit of 1; Coordination environments of (b) [B5O10]5- cluster, (c) [B3O7]5- cluster, and (d) AlO4 tetrahedron

    Color codes: green, [B5O10]5- cluster; yellow, [B3O7]5- cluster; pink, AlO4 tetrahedron; Symmetric codes: #1: 2-x, 2-y, 1-z; #2: 1+x, 1+y, z; #3: x, 1+y, z; #4: -1+x, y, z.

    下载: 全尺寸图片 幻灯片

    Figure 2  (a) View of a 2D monolayer with 8- and 10-MR windows; (b) Porous layer stacked in -AAA- mode

    Color codes: green, [B5O10]5- cluster; yellow, [B3O7]5- cluster; pink, AlO4 tetrahedron.

    下载: 全尺寸图片 幻灯片

    Figure 3  (a) Two types of channels along the a-axis; (b) View of window Ⅰ; (c) View of window Ⅱ; (d-g) Four types of channels along different directions; (h) Six types of intercommunicated channel networks

    Symmetric codes: #1: 1+x, y, z; #2: 1+x, -1+y, z; #3: 3-x, 1-y, 1-z; #4: 2-x, 1-y, 1-z; #5: 2-x, 2-y, 1-z.

    下载: 全尺寸图片 幻灯片

    Figure 4  IR spectrum of 1

    下载: 全尺寸图片 幻灯片

    Figure 5  Experimental and simulated PXRD patterns of 1

    下载: 全尺寸图片 幻灯片

    Figure 6  TGA curve of 1

    下载: 全尺寸图片 幻灯片

    Figure 7  UV-Vis diffuse reflectance spectrum of 1

    Inset: the corresponding bandgap.

    下载: 全尺寸图片 幻灯片

    Table 1.  Crystal data and structure refinements for 1

    Parameter 1 Parameter 1
    Empirical formula Na2.5Rb[Al{B5O10}{B3O5}]·0.5NO3·H2O Z 2
    Formula weight 545.43 Dc / (g·cm-3) 2.412
    Crystal system Triclinic μ/mm-1 3.529
    Space group P1 F(000) 526
    a/nm 0.704 98(5) Reflection collected 8 926
    b/nm 1.031 02(9) Independent reflection 3 679
    c/nm 1.092 17(8) Rint 0.042 2
    α/(°) 103.525(7) Data, restraint, number of parameters 3 679, 46, 295
    β/(°) 98.706(6) Goodness-of-fit on F 2 1.069
    γ/(°) 97.688(6) Final R indices [I > 2σ(I)]a R1=0.043 7, wR2=0.091 1
    V/nm3 0.751 02(10) R indices (all data)b R1=0.064 0, wR2=0.101 7
    a R1=∑||Fo|-|Fc||/∑|Fo|; b wR2=[∑w(Fo2-Fc2)2/∑w(Fo2)2]1/2.
    下载: 导出CSV

    Table 2.  Known octaborates built from {B5} and {B3} sub-clusters

    Formula Space group FBB Sub-cluster Dimension Ref.
    [NH3CH2CH(CH3)NH3][B8O11(OH)4]·H2O P21/c [B8O12(OH)4]4- [B3O6(OH)]4-+[B5O7(OH)3]2- 1D [44]
    [Zn(en)2{B8O11(OH)4}] P1 [B8O12(OH)4]4- [B3O5(OH)2]3-+[B5O8(OH)2]3- 1D [45]
    Li4Ca2[B8O12(OH)4]2·3H2O C2/c [B8O14(OH)4]8- [B3O5(OH)3]4-+[B5O10(OH)]6- 2D [46]
    Na2(H2en)[B5O8(OH)]2[B3O4(OH)]2 P21/c [B8O12(OH)2]2- [B3O6(OH)]4-+[B5O9(OH)]4- 2D [47]
    LiNaB8O13 C2/c [B8O16]8- [B3O7]5-+[B5O10]5- 3D [49]
    α-LiKB8O13 Pbca [B8O16]8- [B3O7]5-+[B5O10]5- 3D [49]
    β-LiKB8O13 P21/c [B8O16]8- [B3O7]5-+[B5O10]5- 3D [49]
    下载: 导出CSV
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  • 发布日期:  2025-01-10
  • 收稿日期:  2024-09-18
  • 修回日期:  2024-11-29
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