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. 2023 Jun 2;8(23):21172–21181. doi: 10.1021/acsomega.3c02248

Three Polyborates with High-Symmetry [B12O24] Units Featuring Different Dimensions of Anion Groups

Yu Dang †,‡, Jingdong Yan †,‡, Xueling Hou †,‡,*, Hongsheng Shi †,‡,*
PMCID: PMC10268625  PMID: 37332783

Abstract

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Three polyborates, namely, LiNa11B28O48, Li1.45Na7.55B21O36, and Li2Na4Ca7Sr2B13O27F9, were synthesized via the high-temperature solution method. All of them feature high-symmetry [B12O24] units, yet their anion groups exhibit distinct dimensions. LiNa11B28O48 features a three-dimensional anionic structure of 3[B28O48]∞ framework, which is composed of three units: [B12O24], [B15O30], and [BO3]. Li1.45Na7.55B21O36 possesses a one-dimensional anionic structure of 1[B21O36]∞ chain consisting of [B12O24] and [B9O18] units. The anionic structure of Li2Na4Ca7Sr2B13O27F9 is composed of two zero-dimensional isolated units, namely, [B12O24] and [BO3]. The novel FBBs [B15O30] and [B21O39] are present in LiNa11B28O48 and Li1.45Na7.55B21O36, respectively. The anionic groups in these compounds exhibit a high degree of polymerization, thereby augmenting the structural diversity of borates. And the crystal structure, synthesis, thermal stability, and optical properties were meticulously discussed to guide the synthesis and characterization of novel polyborates.

Introduction

Borates are extensively utilized in the fields of photoelectric functional materials, glass materials, ceramic materials, fire-resistant materials, and additive materials owing to their diverse structures and exceptional properties.1,2 Among them, photoelectric functional materials play a crucial role in various advanced optical devices such as lasers, polarizers, optical isolators, and photolithography. They have extensive applications in scientific research, military technology, medical treatment, and other fields. In particular, several borates such as BaB2O4 (BBO),3 LiB3O5 (LBO),4 KBe2BO3F2 (KBBF),5 and others have garnered significant attention in the field of nonlinear optical materials over the past century. From the atomic scale, the electron configuration of the boron atom is 1s22s22p1, indicating the presence of one p orbital electron and two unoccupied p orbitals. Therefore, the boron atom can function as an electron acceptor to interact with oxygen atoms, resulting in the formation of linear [BO2], triangular [BO3], and tetrahedral [BO4] basic units. And these basic units can be further polymerized to generate a diverse array of borate structures. With the continuous efforts of scientists worldwide, numerous borates have been discovered in recent years. For example, if the founded borates are arranged in ascending order according to the number of boron atoms in the formula, there are NaBO2,6 BaB2O4, LiB3O5, AB4O6F (A = NH4, Na, Rb, Cs),7−10 MB5O7F3(M = Mg, Ca, Sr),11−13 A2B6O9F2 (A = Li, Na, K, NH4),14−19 Rb3B7O12,20 BaB8O13,21 CsB9O14,22 Ba2B10O17,23 NH4B11O16(OH)2,24 (NH4)4[B12O16F4(OH)4],25 K10B13O15F19,26 Sr3B14O24,27 NH4B15O20(OH)8·4H2O,28 Sr2B16O26,29 Sr8MgB18O36,30 Rb5B19O31,31 Na2Cs2B20O32,32 NaCsB21O36,33 etc. Among them, compounds containing the 12-membered ring [B12O24] unit are popular. There are six [BO4] and six [BO3] on the inside and outside of the [B12O24] unit, respectively. And it can also be viewed as six [B3O8] units up-and-down crossly connected by sharing [BO4] unit. According to the theory of Christ et al.34 and Burns et al.,35 the descriptor of the 12-membered ring [B12O24] unit can be expressed as 12:6Δ + 6T and 6Δ6□:≪Δ2□>-•>. As far as current knowledge goes, Na8[B12O20(OH)4] was the first borate to contain the [B12O24] unit, discovered in 1979.36 Subsequently, silver borate Ag6[B12O18(OH)6]·3H2O was found in 1990,37 followed by zinc borate Zn(H2O)B2O4·xH2O38 in 2002 and K7{(BO3)Mn[B12O18(OH)6]}·H2O in 2004.39 And Li3NaBaB6O12,41 Li3KB4O8, LiNa2Sr8B12O24F6Cl,42 Li7Na2KRb2B12O24, Li7.35Na2.36K1.50Cs0.78B12O24, Li6.97Na2.63K1.24Cs1.15B12O24, Li7.27Na2.67Rb2.06B12O24,43 Ca3Na4LiBe4B10O24F,44 Sr3LiNa4Be4B10O24F,45 and Li6.58Na7.43Sr4(B9O18)(B12O24)Cl46 were all discovered after 2010. The majority of the aforementioned compounds are anhydrous borates featuring the [B12O24] unit. Additionally, most of these structures exhibit centrosymmetry and are arranged in a nonparallel, isolated manner.

In this paper, three polyborates featuring [B12O24] unit were synthesized via the high-temperature solution method. Their anionic groups exhibit distinct dimensions. LiNa11B28O48 features a novel 3[B28O48]∞ framework anion structure, which is constructed by [B12O24], [B15O30], and [BO3] units through sharing of corner O atoms. Li1.45Na7.55B21O36 exhibits a unique 1[B21O36]∞ chain anion structure, built by [B12O24] and [B9O18] units through sharing of corner O atoms. New FBBs, namely, [B15O30] and [B21O39], have been identified in LiNa11B28O48 and Li1.45Na7.55B21O36, respectively. Li2Na4Ca7Sr2B13O27F9 is a borate with an isolated anion structure composed of [B12O24] and [BO3] units. Furthermore, we conducted a detailed comparison of these structures with other borates containing the [B12O24] unit in order to investigate their structural commonalities and differences. The thermal stability and optical properties of these three compounds were evaluated to assess their suitability for further application.

Experimental Section

Single-Crystal Synthesis

Single crystals of LiNa11B28O48, Li1.45Na7.55B21O36, and Li2Na4Ca7Sr2B13O27F9 were obtained via the high-temperature solution method with specific synthesis details as follows:

LiNa11B28O48

A mixture of LiBO2 (0.079 g, 0.99 mmol), NaF (0.161 g, 3.83 mmol), and H3BO3 (0.125 g, 2.02 mmol) was enclosed in a clean silica quartz tube with dimensions of Φ10 mm × 100 mm. The NaF served as both a co-solvent and the source of Na in LiNa11B28O48. The sample was gradually heated to 650 °C over a period of 24 h and held at this temperature for an additional 48 h to ensure complete melting. Subsequently, the solution was slowly cooled to room temperature at a rate of 1.5 °C/h. Finally, the colorless crystals of LiNa11B28O48 can be selectively harvested from the resulting product.

Li1.45Na7.55B21O36

A mixture of LiBF4 (0.316 g, 3.37 mmol), NaF (0.47 g, 11.19 mmol), Y2O3 (0.291 g, 1.29 mmol), and B2O3 (0.975 g, 14.00 mmol) was charged into a platinum crucible wherein Y2O3 acted as the catalyst for the reaction while NaF served as both co-solvent and source of Na for Li1.45Na7.55B21O36. The samples were gradually heated at a rate of 100 °C/h from room temperature to 750 °C and held at this temperature for 24 h to guarantee full dissolution. Subsequently, the solution was slowly cooled down to 500 °C with a cooling rate of 1.5 °C/h, followed by rapid cooling to room temperature at a rate of 5 °C/h. Finally, small transparent thin crystals of Li1.45Na7.55B21O36 were picked out from the obtained samples.

Li2Na4Ca7Sr2B13O27F9

Li2Na4Ca7Sr2B13O27F9 was synthesized using a similar process as Li1.45Na7.55B21O36, with a mixture of LiF (0.108 g, 4.16 mmol), Na2CO3 (0.184 g, 1.74 mmol), CaF2 (0.267 g, 3.42 mmol), SrF2 (0.443 g, 3.53 mmol), H3BO3 (0.553 g, 8.94 mmol), PbO (0.194 g, 0.87 mmol), and PbF2 (0.292 g, 1.19 mmol). The inclusion of PbO and PbF2 in the reaction served as cosolvents but were not incorporated into the final structure.

Polycrystalline Powder Synthesis

Polycrystalline samples of these three compounds can be synthesized via the high-temperature solid-state reactions as the equation below

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The initial raw materials, in stoichiometric ratio as per the reaction equation of three compounds mentioned above, were thoroughly mixed and filled into a ceramic crucible. Then, the samples were gradually heated to 300 °C over a period of 6 h and maintained at that temperature for 10 h in order to decompose H3BO3 and remove gases such as H2O and CO2. Subsequently, the preheated mixture was subjected to heated to 640 °C and held at that temperature for 72 h with intermittent grinding and mixing. Finally, turn off the stove and allow the sample to cool naturally. Pure polycrystalline powder of LiNa11B28O48 and Li1.45Na7.55B21O36 were obtained. However, as shown in Figure 5, despite our best efforts, the polycrystalline powder of Li2Na4Ca7Sr2B13O27F9 we obtained was not entirely pure.

Figure 5.

Figure 5

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Calculated (black lines) and experimental (red lines) powder XRD patterns of LiNa11B28O48, Li1.45Na7.55B21O36, and Li2Na4Ca7Sr2B13O27F9.

Powder X-ray Diffraction

The purity of the polycrystalline powders of these three compounds was assessed using a Bruker D2 PHASER powder X-ray diffractometer (PXRD). Diffraction data were collected over a 2θ range of 5–70°, with a scan rate of 0.05 s/step and a scan step size of 0.02°.

Single-Crystal X-ray Diffraction

High-quality colorless single crystals were selected for single-crystal X-ray diffraction (XRD) tests. The diffraction data were collected using a Bruker D8 VENTURE single-crystal X-ray diffractometer with Cu Kα radiation (λ = 1.54178 Å) at 297.15 K for LiNa11B28O48 and Mo Kα radiation (λ = 0.71073 Å) at 273.15 K for Li1.45Na7.55B21O36, Li2Na4Ca7Sr2B13O27F9. The APEX3 software, which is compatible with the diffractometer, was utilized for data reduction and analysis. These structures were solved with the SHELXT program through the intrinsic phasing method, refined by the full matrix least squares method in the SHELXL program, and checked for symmetry via PLATON program in Olex2. Table 1 provides detailed information on crystal and structure refinement data. The final atomic coordinates, equivalent isotropic displacement parameters, bond valence sum (BVS) for each atom, as well as the selected bond lengths and angles in compounds are listed in Tables S1–S9 in the Supplementary Information (ESI).

Table 1. Crystal and Structure Refinement Data.

empirical formula LiNa11B28O48 Li1.45Na7.55B21O36 Li2Na4Ca7Sr2B13O27F9
temperature 297.15 K 273.15 K 273.15 K
crystal system, space group hexagonal, P63/mcm hexagonal, P63/mcm hexagonal, P63/m
unit cell dimensions a = 9.50430(10) Å a = 9.3446(3) Å a = 9.32940(10) Å
b = 9.50430(10) Å b = 9.3446(3) Å b = 9.32940(10) Å
c = 25.0041(3) Å c = 20.2013(10) Å b = 19.5978(5) Å
volume 1956.06(5) Å3 1527.68(12) Å3 1477.22(5) Å3
Z, calculated density 2, 2.259 g·cm–3 2, 2.145 g·cm–3 2, 2.934 g·cm–3
crystal size 0.059 × 0.078 × 0.081 mm3 0.11 × 0.12 × 0.15 mm3 0.102 × 0.103 × 0.112 mm3
absorption coefficient 2.894 mm–1 0.286 mm–1 5.053 mm–1
F (000) 1296 961 1256
radiation Cu Kα (λ = 1.54178) Mo Kα (λ = 0.71073) Mo Kα (λ = 0.71073)
θ range for data collection 3.54 to 68.3° 2.016 to 17.483° 2.016 to 17.483°
limiting indices –11 ≤ h ≤ 10, –9 ≤ k ≤ 11, –19 ≤ l ≤ 30 –12 ≤ h ≤ 12, –11 ≤ k ≤ 12, –26 ≤ l ≤ 26 –9 ≤ h ≤ 12, –12 ≤ k ≤ 12, –25 ≤ l ≤ 25
reflections collected/unique 14 995/688 [Rint = 0.0578] 11 789/669 [Rint = 0.0862] 9997/1164 [Rint = 0.0390]
data/restraints/parameters 688/6/96 669/0/69 1164/0/104
goodness-of-fit on F2 1.216 1.031 1.155
final R indices [Fo2 > 2σ(Fo2)]a R1 = 0.0625, wR2 = 0.1347 R1 = 0.0321, wR2 = 0.0851 R1 = 0.0290, wR2 = 0.0769
largest diff. peak and hole 0.44 and –0.63 e·Å–3 0.91 and –0.76 e·Å–3 1.09 and –0.68 e·Å–3
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a

R1 = ∑||Fo| – |F|| / ∑|Fo| and wR2 = [∑w(Fo2 – Fc2)2 / ∑wFo4]1/2 for Fo2 > 2σ(Fo2).

Infrared Spectroscopy

A Shimadzu IR Affinity-11 FT-IR spectrometer was utilized for the infrared (IR) spectroscopy analysis to identify characteristic peaks and verify the rationality of these three structures. Data were collected within a range of 400 to 4000 cm–1 with a resolution set at 1 cm–1. These samples were homogeneously mixed with dried KBr at a ratio of 1:100 for testing purposes, while pure KBr was employed to eliminate air noise-induced peaks.

Energy-Dispersive X-ray Spectroscopy

Elemental analysis was used to identify the constituent elements of the crystal composition. The test was performed utilizing a BRUKER X-flash-sdd-5010 energy-dispersive X-ray spectroscope (EDS) integrated into a SUPRA 55 VP field emission scanning electron microscope (SEM).

UV–Vis–NIR Diffuse Reflectance Spectroscopy

The transmittance range of these compounds was evaluated using UV–vis–NIR diffuse reflectance spectroscopy, with a Shimadzu SolidSpec-3700DUV spectrophotometer employed for the test. Data were collected at room temperature over a wavelength range of 200–2600 nm, with tetrafluoroethylene serving as the standard sample for the diffuse reflectance test.

TG-DSC Analyses

Thermogravimetry (TG) and differential scanning calorimetry (DSC) tests were performed to investigate the thermal stability of these three compounds. The simultaneous NETZSCH STA 449 F3 thermal analyzer instrument was utilized for testing, with samples of the three compounds placed in a Pt crucible and heated from 40 to 800 °C at a rate of 5 °C·min–1 under a nitrogen atmosphere. The equipment recorded weight and thermal energy changes as the temperature changed.

Results and Discussion

Structural Structure

LiNa11B28O48 crystallizes in a hexagonal crystal system with space group P63/mcm (No. 193). LiNa11B28O48 is composed of [LiO6], [NaO6], [NaO7], [BO3], and [BO4] units. [BO3] and [BO4] connect through corner O atoms to form polyborates of [B15O30] and [B12O24]. To the best of our knowledge, the [B15O30] unit represents a novel fundamental building block (FBB). Moreover, through sharing corner O atoms, [B15O30] and [B12O24] construct tunnels of [B27O51]. These tunnels are further linked by [BO3] to form the overall anionic framework of 3[B28O48]∞ in LiNa11B28O48 (Figure 1). In the structure, the B–O bond length in [BO3] units ranges from 1.35 to 1.49 Å, whereas the B–O bond length in [BO4] units ranges from 1.43 to 1.59 Å. The Li atoms are coordinated by six oxygen atoms to form [LiO6] octahedra, with a constant Li–O bond distance of 2.11 Å. The Na atoms exhibit two distinct coordination environments, namely, [NaO6] and [NaO7] polyhedra, with Na–O bond distances ranging from 2.23 to 2.93 Å (Figure S1).

Figure 1.

Figure 1

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Anion group in three dimensions and the novel FBB [B15O30] in LiNa11B28O48.

Li1.45Na7.55B21O36 crystallizes in the hexagonal crystal system with space group P63/mcm (No. 193). Li1.45Na7.55B21O36 is composed of [LiO6], [Na(Li)O6], [NaO7], [BO3], and [BO4] units. [BO3] and [BO4] connect to form polyborates of [B9O18] and [B12O24] by sharing corner O atoms. Furthermore, these polyborates combine to create an FBB of [B21O39]. It should be noted that this particular FBB has not been previously reported. These FBBs are interconnected to form the anionic chain of 1[B21O36]∞ in Li1.45Na7.55B21O36 (Figure 2). Interestingly, it differs from that in the recently published compound Li6.58Na7.43Sr4(B9O18)(B12O24)Cl, where [B9O18] and [B12O24] units exist as isolated clusters. In the structure, [BO3] units with three-fold coordination exhibit B–O bond distances ranging from 1.34 to 1.42 Å, while [BO4] units with four-fold coordination possess B–O bond distances within the range of 1.44–1.51 Å. The bond distances of Na(Li)–O in [Na(Li)O6] octahedra exhibit a range from 2.300 to 2.301 Å, while the Li–O bond lengths in [LiO6] octahedra remain constant at 2.101 Å. The Na–O bond distances in [NaO7] vary from 2.291 to 2.917 Å (Figure S2).

Figure 2.

Figure 2

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Anion group in one dimension and the novel FBB [B21O39] in Li1.45Na7.55B21O36.

Li2Na4Ca7Sr2B13O27F9 crystallizes in the hexagonal crystal system with space group P63/m (No. 176). Li2Na4Ca7Sr2B13O27F9 is composed of [LiO6], [LiF6], [NaO6], [CaO4F4], [Ca(Sr)O5F3], [BO3], and [B12O24] units. In contrast to the preceding two compounds, Li2Na4Ca7Sr2B13O27F9 features discrete anionic groups in the form of [BO3] and [B12O24] units (Figure 3). In the structure, the B–O bond distances within the [BO3] units exhibit a range of 1.33–1.41 Å, while those within the [BO4] units display a range of 1.46 to 1.49 Å (Figure S3). The Li–O bond and Li–F bond distances in [LiO6] and [LiF6] octahedra take the constant value of 2.104 and 2.103 Å, respectively. The bond distances of Na–O in [NaO6] exhibit a range of 2.299 to 2.588 Å. In [Ca(Sr)O5F3], the bond distances of Ca(Sr)–O stretch from 2.42 to 3.24 Å, while the Ca(Sr)–F vary from 2.34 to 2.56 Å. Similarly, the Ca–O bond distances vary from 2.36 to 2.70 Å and Ca–F bond stretch from 2.39 to 2.48 Å in [CaO4F4] (Figure S4).

Figure 3.

Figure 3

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Anion group in zero dimension in Li2Na4Ca7Sr2B13O27F9.

These three compounds all contain high-symmetry 12-membered ring [B12O24] units. Through an investigation of published borates containing [B12O24] units, a total of 20 cases have been identified to date (including the three compounds in this study) (Table 2). As depicted in the table, fundamental crystal structure data have been succinctly summarized, and for ease of subsequent discourse, Arabic numerals were assigned to the 20 compounds. Notably, intriguing patterns exist among these borates featuring the ring-like [B12O24] unit. First, with the exception of hydroxyl-containing borates (No.1–5) and recently discovered borates (No. 17–20), most crystallize in the same R3̅ space group (No.6–16). Previous research and analysis suggest that this is primarily due to the local symmetry 3̅ of the [B12O24] units within their structure.46 And for exceptional cases, it is primarily due to the introduction of hydroxyl or other group that can disrupt the symmetry of [B12O24] units, such as the [B12O20(OH)4] unit in Na8[B12O20(OH)4], the [B12O18(OH)6] unit in Ag6[B12O18(OH)6]·3H2O. In this study, LiNa11B28O48, Li1.45Na7.55B21O36 have a space group of P63/mcm and the space group of Li2Na4Ca7Sr2B13O27F9 is P63/m. Likewise, it is [B15O30] unit in LiNa11B28O48, [B9O18] unit in Li1.45Na7.55B21O36, and [BO3] unit in Li2Na4Ca7Sr2B13O27F9 that break the symmetry of [B12O24] units and change the space group of compounds. Second, except compounds of No. 1–5, the values of a and b are equivalent, both exceeding 9 Å, and the value of c is approximately 20 Å, which significantly surpasses a and b in their cell parameters. This pertains to the crystal system of the crystallographic space group of these compounds. Third, this series of compounds with the ring-like [B12O24] units all contain Li and Na elements with the exception of compounds No. 2–5. Moreover, the anion groups of these compounds exhibit distinct dimensions and most of them are isolated structures. Based on the borate anion dimension theory proposed by P. Becker and N. I. Leonyuk,48,49 the dimension of borate anion groups is often influenced by the M/B ratio, with a higher M/B ratio leading to a smaller dimension of the anion group (where M and the B represent the stoichiometric number of metal and boron in this compound). The borates containing [B12O24] units also adhere to this principle. As indicated in the penultimate column of Table 2, with the exception of LiNa11B28O48 and Li1.45Na7.55B21O36 discovered in this study, all other borates listed have isolated anion groups, and their M/B ratios are greater than 1/2. The LiNa11B28O48 and Li1.45Na7.55B21O36 exhibit a three-dimensional framework structure and a one-dimensional chain structure, with both having an M/B ratio of 3/7, which is lower than that of the isolated ones.

Table 2. Basic Information of Inorganic Borates with Ring-like B12O24 Clusters.

no. chemical formula space group B–O units cell parameters M/B refs
1 Na8[B12O20(OH)4] P21/c(14) [B12O20(OH)4] a = 8.709 Å; b = 11.917 Å; c = 9.468 Å 2/3 (36)
α = γ = 90°; β = 96.02°
2 Ag6[B12O18(OH)6]·3H2O P21/c(14) [B12O18(OH)6] a = 11.784 Å; b = 10.654 Å; c = 9.468 Å 1/2 (37)
α = γ = 90°; β = 96.02°
3 Zn(H2O)B2O4·xH2O(x ≈ 0.12) R3̅m(166) [B12O24] a = b = 11.410 Å; c = 17.156Å 1/2 (38)
α = β = 90°; γ = 120°
4 K7{(BO3)Mn[B12O18(OH)6]}·H2O Pmn21(31) [B12O20(OH)4] + [BO3] a = 12.397 Å; b = 9.1185 Å; c = 13.068 Å 8/13 (39)
α = β = γ = 90°
5 K7{(BO3)Zn[B12O18(OH)6]}·H2O Pmn21(31) [B12O20(OH)4] + [BO3] a = 12.365 Å; b = 9.096 Å; c = 13.041 Å 8/13 (40)
α = β = γ = 90°
6 Li3NaBaB6O12 R3̅(148) [B12O24] a = b = 9.462 Å; c = 18.71 Å 5/6 (41)
α = β = 90°; γ = 120°
7 Li3KB4O8 R3̅(148) [B12O24] a = b = 9.211 Å; c = 19.705 Å 1/1 (42)
α = β = 90°; γ = 120°
8 LiNa2Sr8B12O24F6Cl R3̅(148) [B12O24] a = b = 9.677 Å; c = 24.30 Å 11/12 (42)
α = β = 90°; γ = 120°
9 Ca3Na4LiBe4B10O24F R3̅(148) [B12O24] + [BO3] a = b = 9.354 Å; c = 38.053 Å 6/5 (44)
α = β = 90°; γ = 120°
10 Sr3LiNa4Be4B10O24F R3̅(148) [B12O24] + [BO3] a = b = 9.4645 Å; c = 38.842 Å 6/5 (45)
α = β = 90°; γ = 120°
11 Cd3LiNa4Be4B10O24F R3̅(148) [B12O24] + [BO3] a = b = 9.302 Å; c = 37.782 Å 6/5 (45)
α = β = 90°; γ = 120°
12 Na5Li[B12O18(OH)6]·2H2O R3̅c(167) [B12O18(OH)6] a = b = 9.677 Å; c = 36.358 Å 1/2 (47)
α = β = 90°; γ = 120°
13 Li7Na2KRb2B12O24 R3̅(148) [B12O24] a = b = 9.548 Å; c = 19.55 Å 1 (43)
α = β = 90°; γ = 120°
14 Li7.35Na2.36K1.50Cs0.78B12O24 R3̅(148) [B12O24] a = b = 9.479 Å; c = 19.493 Å 1 (43)
α = β = 90°; γ = 120°
15 Li6.97Na2.63K1.24Cs1.15B12O24 R3̅(148) [B12O24] a = b = 9.530 Å; c = 19.534 Å 1 (43)
α = β = 90°; γ = 120°
16 Li7.27Na2.67Rb2.06B12O24 R3̅(148) [B12O24] a = b = 9.453 Å; c = 19.413 Å 1 (43)
α = β = 90°; γ = 120°
17 Li6.58Na7.43Sr4(B9O18)(B12O24)Cl P63/m(176) [B12O24] + [B9O18] a = b = 9.305 Å; c = 24.324 Å 6/7 (46)
α = β = 90°; γ = 120°
18 LiNa11B28O48 P63/mcm(193) [B12O24 + B15O30 + BO3] a = b = 9.504 Å; c = 25.0038 Å 3/7 this work
α = β = 90°; γ = 120°
19 Li1.45Na7.55B21O36 P63/mcm(193) [B12O24 + B9O18] a = b = 9.345 Å; c = 20.201 Å 3/7 this work
α = β = 90°; γ = 120°
20 Li2Na4Ca7Sr2B13O27F9 P63/m(176) [B12O24] + [BO3] a = b = 9.329 Å; c = 19.598 Å 15/13 this work
α = β = 90°; γ = 120°
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During the survey process, four additional configurations of [B12O24] units were also discovered in Cs3AlB6O12,50 Ba4Na2Zn4(B3O6)2(B12O24),51 pringleite mineral Ca9B26O34(OH)24Cl4·13H2O,52 and KB3O4(OH)2.53 They differ from the [B12O24] units mentioned in this paper. As depicted in Figure 4, these five distinct [B12O24] units exhibit varying ring-shaped structures composed of twelve boron atoms and twenty-four oxygen atoms. However, the connectivity patterns among these constituent elements differ significantly. The [B12O24] unit in Ba4Na2Zn4(B3O6)2(B12O24) (Figure 4c) and this paper (Figure 4a) are both made up of six [BO3] and six [BO4], so the topological descriptor of them can be represented as 12:8Δ + 4T using the method of Christ and Clark. However, the [B12O24] unit in this study is composed of one 12-membered ring and six 6-membered rings and can be represented as 6Δ6□:≪Δ2□>-•> on the description theory of Burns. The [B12O24] unit of Ba4Na2Zn4(B3O6)2(B12O24) (Figure 4c) expands to a 24-membered ring and can be described as 6Δ6□:<Δ□•>. The [B12O24] units in Cs3AlB6O12 (Figure 4b), Ca9B26O34(OH)24Cl4·13H2O (Figure 4d), and KB3O4(OH)2 (Figure 4e) are constructed by eight [BO3] and four [BO4]; thus, they can be expressed as 12:8Δ + 4T according to the method of Christ and Clark. However, they exhibit significant differences with several distinct rings. The [B12O24] unit in Cs3AlB6O12 contains four 6-membered rings and one 8-membered ring; thus, the detailed descriptor of the structure is 8Δ4□:<2Δ□>-<Δ2□>-<2Δ2□>-<Δ2□>-<2Δ□> (Figure 4b). The [B12O24] unit in Ca9B26O34(OH)24Cl4·13H2O is composed of four 6-membered rings and one 4-membered ring, which can be represented as 2×{2×(3[2Δ + 1T])} (Figure 4d). And the [B12O24] unit in KB3O4(OH)2 is constructed by four 6-membered rings and one 16-membered ring; thus, the detailed descriptor is 8Δ4□:≪2Δ□>•>. Additionally, hydrogen atoms are bonded to the dangling oxygen atoms within this unit (Figure 4e). To have a picture of all these [B12O24] units exhibiting distinct structures, the [B12O24] unit present in our three compounds demonstrates the highest degree of symmetry (Figure 4a).

Figure 4.

Figure 4

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Different [B12O24] units and their topological representation in (a) Li3KB4O8, (b) Cs3AlB6O12, (c) Ba4Na2Zn4(B3O6)2(B12O24), (d) Ca9B26O34(OH)24Cl4·13H2O, and (e) KB3O4(OH)2.

Phase Identification and Analysis

The bond valence sum (Tables S1, S4, and S7) and conventional structural configuration of three- and four-coordinated B–O units (Tables S2, S5, and S8) provide preliminary confirmation of the structural rationality of the three compounds. Powder XRD confirmed the phase purity of these samples (Figure 5). And as shown in Figure S5, the IR spectrum well verified the existence of [BO3] and [BO4] units in structures, which was consistent with results obtained from single-crystal XRD analysis. According to previous research,54 the stretching vibration signals of the [BO3] can be observed within the spectral range of 1396–1419 cm–1. The asymmetric stretching signals of the B–O bond in [BO3] appear between 1234 and 1273 cm–1. The asymmetric stretching signals of the B–O bond in [BO4] can be observed within the range of 1026–1041 cm–1, while the symmetric stretching signals of the B–O bond in [BO3] are present between 887 and 964 cm–1. Additionally, out-of-plane bending modes of both [BO3] and [BO4] can be detected within a range of 628 to 740 cm–1. The elemental analysis revealed the presence of fluorine elements in Li2Na4Ca7Sr2B13O27F9 (Figure S6).

Thermal and Optical Properties

The thermostability test results of samples are depicted in the TG and DSC curves (Figure 6). The TG curves of the three samples exhibited no significant decrease in their curves, indicating that there was no substantial weight loss during the heating process. Additionally, distinct endothermic peaks were observed for all three compounds after 700 °C in the DSC curves, demonstrating their thermal stability up to this temperature. The diffuse reflectance spectra of the three compounds exhibit negligible absorption within the range of 266–2500 nm, indicating their high ultraviolet transmittance among these regions (Figure 6). There are two explanations for this phenomenon: (1) The absence of d–d and f–f electronic transitions in these compounds facilitates transmission in the UV region; (2) High polymerized B–O groups effectively eliminate dangling bonds of O atoms in the anionic framework of three compounds. Notably, the UV cutoff edge of Li2Na4Ca7Sr2B13O27F9 is 241 nm, which is shorter than that of the other two compounds. This can be attributed to the high electronegativity of F.55

Figure 6.

Figure 6

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TG-DSC curves and UV–vis–NIR diffuse reflectance spectra of LiNa11B28O48 (a, d), Li1.45Na7.55B21O36 (b, e), and Li2Na4Ca7Sr2B13O27F9 (c, f).

Conclusions

In summary, two borates and one borate fluoride with highly symmetrical [B12O24] units were successfully synthesized via the high-temperature solution method. These three compounds exhibit anion groups ranging from three-dimensional to zero-dimensional structures. The correlation between the M/B ratio and structure dimension of compounds containing ring-like [B12O24] units was discussed. The LiNa11B28O48 compound contains a [B15O30] unit, while the Li1.45Na7.55B21O36 compound features a [B21O36] unit, both of which are novel FBBs with highly polymerized anion groups that enhance the structural diversity of borates. Besides, they exhibit thermal stability up to 700 °C and possess the ability of ultraviolet transmission. The exceptional thermal and optical properties render them advantageous for further applications.

Acknowledgments

This work was supported by the Xinjiang Senior Talents Program, the Xinjiang Major Science and Technology Project (2022A01005).

Supporting Information Available

The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsomega.3c02248.

  • Table of atomic coordinates, equivalent isotropic displacement parameters, bond valence sum, selected bond distances and angles, asymmetric unit, and atomic coordination environment of three compounds (PDF)

  • Crystallographic data 1 (CIF)

  • Crystallographic data 2 (CIF)

  • Crystallographic data 3 (CIF)

Accession Codes

CCDC 2233774, 2233775, and 2233776 contain the supplementary crystallographic data for LiNa11B28O48, Li1.45Na7.55B21O36, and Li2Na4Ca7Sr2B13O27F9. The data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, by emailing data_request@ccdc.cam.ac.uk, or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, U.K.; fax: + 44 1223 336033.

Author Contributions

# Y.D. and J.Y. contributed equally to this work.

The authors declare no competing financial interest.

Supplementary Material

ao3c02248_si_001.pdf (926.3KB, pdf)
ao3c02248_si_002.cif (528.3KB, cif)
ao3c02248_si_003.cif (410.7KB, cif)
ao3c02248_si_004.cif (333.6KB, cif)

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Supplementary Materials

ao3c02248_si_001.pdf (926.3KB, pdf)
ao3c02248_si_002.cif (528.3KB, cif)
ao3c02248_si_003.cif (410.7KB, cif)
ao3c02248_si_004.cif (333.6KB, cif)

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