Rare-Earth Borate-Sulfates Featuring Three Types ... - ACS Publications

Dec 14, 2017 - RE(SO4)[B(OH)4](H2O), RE(SO4)[B(OH)4](H2O)2, and RE(SO4)[B(OH)4](H2O)·H2O: Rare-Earth Borate-Sulfates Featuring Three Types of Layered...
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Article Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX

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RE(SO4)[B(OH)4](H2O), RE(SO4)[B(OH)4](H2O)2, and RE(SO4)[B(OH)4](H2O)·H2O: Rare-Earth Borate-Sulfates Featuring Three Types of Layered Structures Wen-Wen Wang,†,‡ Xiang Xu,*,† Jin-Tao Kong,§ and Jiang-Gao Mao*,† †

State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, People’s Republic of China ‡ College of Chemistry, Fuzhou University, Fuzhou 350108, People’s Republic of China § Key Laboratory of Optoelectronic Materials Chemistry and Physics, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, People’s Republic of China S Supporting Information *

ABSTRACT: Using hydrothermal reactions, three series of rare-earth borate-sulfates, namely, RE(SO4)[B(OH)4](H2O) (RE = La (1), Sm (2), Eu (3)), RE(SO4)[B(OH)4](H2O)2 (RE = Pr (4), Nd (5), Sm (6), Eu (7), Gd (8)), and RE(SO4)[B(OH)4](H2O)·H2O (RE = Tb (9), Dy (10), Ho (11), Er (12), Tm (13), Yb (14), Lu (15), Y (16)), have been synthesized, which represent the first rare-earth boratesulfate mixed-anion compounds. All these compounds possess the same fundamental building anionic units of SO4 and B(OH)4 tetrahedra; however, they exhibit three different types of twodimensional (2D) layered structures composed of 1D RE−B−O and RE−S−O chains. The rare-earth borate chains are similar in all compounds, while the rare-earth sulfate chains differ in each type of compound due to the various coordination modes of sulfate groups. On the basis of the measured UV−vis diffuse reflectance spectra, the optical band gaps of compounds 2, 3, 6, and 7 are estimated to be 4.66, 4.53, 4.62, and 4.50 eV, respectively. Luminescence studies show that compounds 2, 3, 6, and 7 exhibit strong emission in the orange or red regions. Furthermore, thermal analysis and magnetic susceptibility measurements for these four representative compounds have also been performed.

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INTRODUCTION Borates are an attractive family of solid-state compounds owing to their rich structural chemistry and interesting physical properties, such as nonlinear optics, luminescence, and anomalous thermal expansion properties.1−21 Over the past few decades, introducing oxo anions of post-transition groups (AlO6, GaO6, GeO4, PO4, SeO3, TeO6, etc.) into the borates has been reported to be an effective strategy to expand the borate family. This strategy has afforded a series of borate derivatives, such as galloborate, borogermanate, boroselenite, borophosphate, borate-phosphate, etc.22−35 Recently, through the combination of BO4 and SO4 anionic groups, borosulfates have been developed as a new class of borates.36−43 In 2012, K5[B(SO4)4] was synthesized and structurally characterized, which repents the first borosulfate,36 and then a series of other borosulfates have been reported, including B2S2O9,37 A3[B(SO4)3] (A = K, Rb),38 A[B(SO4)2] (A = H3O, NH4, Li, Na, K),38−40 A[B(S2O7)2] (A = NH4, Li, Na, K),38−40 A[B(S2O7)(SO4)] (A = H, Cs),39 Cs2B2S3O13,41 Rb4[B2O(SO4)4],41 A5[B(SO4)4] (A = Li, Na, Rb),38,40,43 K4[BS4O15(OH)],42 Ba[B2S3O13],42 and Gd2[B2S6O24].42 The structures of these borosulfates possess a common feature: the BO4 and SO4 groups © XXXX American Chemical Society

are interconnected via corner sharing. Various types of B−S−O anionic structures have been observed, such as the isolated [B(SO4)4]5− unit in Na5[B(SO4)4], one-dimensional (1D) [B(SO4)3]3− chain in K3[B(SO4)3], and 3D [B(SO4)2]− anionic framework in Li[B(S2O7)2].38 As a close relative of the borosulfate, borate-sulfates also contain both borate and sulfate groups, but they are isolated from each other. Up to now, reports on borate-sulfates are rare, and only seven borate-sulfates, namely, Pb6O2(BO3)2(SO4),44 Na2Ca3(B5O8)(SO4)2(OH)2Cl,45 A3H(SO4)2(B2O3)2 (A = Rb, Cs),41 Mg3(OH)2(SO4)[B(OH)4]2,46 Mg3[(OH)4]2(SO4)(OH)F,47 and Ca6Al2(SO4)2[B(OH)4](OH,O)12(H2O)26,48 have been structurally characterized. The boron forms a BO3 triangle in Pb6O2(BO3)2(SO4) and A3H(SO4)2(B2O3)2 (A = Rb, Cs), whereas it forms a BO4 tetrahedron in Mg3(OH)2(SO4)[B(OH)4]2, Mg3[B(OH)4]2(SO4)(OH)F, and Ca6Al2(SO4)2[B(OH)4](OH,O)12(H2O)26. However, both BO3 and BO4 groups are present in Na2Ca3(B5O8)(SO4)2(OH)2Cl. Interestingly, the BO3 groups are condensed into a 2D [B2O3] layer via common Received: September 8, 2017

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DOI: 10.1021/acs.inorgchem.7b02317 Inorg. Chem. XXXX, XXX, XXX−XXX

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Table 1. Crystallographic Data for RE(SO4)[B(OH)4](H2O) (RE = La (1), Sm (2), Eu (3)) and RE(SO4)[B(OH)4](H2O)2 (RE = Pr (4), Nd (5), Sm (6), Eu (7), Gd (8)) RE(SO4)[B(OH)4](H2O) fw space group a (Å) b (Å) c (Å) α (deg) β (deg) γ (deg) V (Å3) Z ρcalcd (g cm−3) μ (mm−1) Rint GOF on F2 R1, wR2 (I > 2σ(I))a R1, wR2 (all data) a

RE(SO4)[B(OH)4](H2O)2

RE = La (1)

RE = Sm (2)

RE = Eu (3)

RE = Pr (4)

RE = Nd (5)

RE = Sm (6)

RE = Eu (7)

RE = Gd (8)

331.83 P1̅ 6.2808(4) 6.8321(4) 8.6830(5) 82.475(5) 76.758(5) 87.300(5) 359.51(4) 2 3.065 6.250 0.0424 1.037 0.0228, 0.0508 0.0266, 0.0522

343.27 P1̅ 6.1467(5) 6.7280(6) 8.6068(7) 81.769(7) 76.653(7) 87.259(7) 342.71(5) 2 3.326 8.891 0.0764 1.026 0.0307, 0.0579 0.0375, 0.0615

344.88 P1̅ 6.1205(4) 6.7090(6) 8.5844(8) 81.713(8) 76.680(7) 87.294(6) 339.40(5) 2 3.375 9.567 0.0282 1.069 0.0222, 0.0509 0.0232, 0.0516

351.84 P21/m 6.2359(5) 9.5542(9) 6.8236(6) 90 93.872(8) 90 405.62(6) 2 2.881 6.296 0.0422 1.067 0.0261, 0.0563 0.0296, 0.0579

355.17 P21/m 6.2119(6) 9.5328(10) 6.7923(6) 90 93.755(9) 90 401.35(7) 2 2.939 6.761 0.0505 1.075 0.0377, 0.0848 0.0436, 0.0883

361.30 P21/m 6.1601(7) 9.5416(13) 6.7589(7) 90 93.816(11) 90 396.39(8) 2 3.027 7.704 0.0727 1.042 0.0363, 0.0744 0.0446, 0.0784

362.89 P21/m 6.1322(4) 9.5139(8) 6.7343(6) 90 93.683(7) 90 392.08(5) 2 3.074 8.299 0.0448 1.077 0.0255, 0.0545 0.0288, 0.0566

368.19 P21/m 6.1148(4) 9.5078(7) 6.7164(5) 90 93.611(6) 90 389.70(5) 2 3.138 8.811 0.0357 1.038 0.0262, 0.0640 0.0290, 0.0664

R1 = ∑||Fo| − |Fc||/∑|Fo|; wR2 = {∑w[(Fo)2 − (Fc)2]2/∑w[(Fo)2]2}1/2. Syntheses. Compounds 1−16 were synthesized by a hydrothermal method with similar procedures. The typical loaded compositions for each compound are given in Table S1 in the Supporting Information. A mixture of the corresponding rare-earth oxide, H3BO3, H2SO4, and H2O was sealed in an autoclave equipped with a 25 mL Teflon lining and heated at 230 °C for compounds 2 and 3 or 220 °C for all other compounds for 72 h, followed by slow cooling to room temperature at a rate of 3 °C h−1. After washing with deionized water, transparent crystals of each compound were obtained. The energy-dispersive spectrometry (EDS) elemental analyses on single crystals of each compound confirmed the presence of S, B, and the corresponding rare-earth element, and the determined average atomic ratio RE to S for all compounds matched well with those determined from single-crystal Xray structural analyses (Figure S1 in the Supporting Information). On the basis of the above optimized synthesis procedures, only Smcontaining compounds (2 and 6) and Eu-containing compounds (3 and 7) have been obtained as pure phases. It is notable that the two Smcontaining compounds and the two Eu-containing compounds could be isolated through adjustment of the reaction conditions such as reaction temperature and molar ratios of the reactants. The yields were about 80%, 82%, 75%, and 79% for compounds 2, 3, 6, and 7 on the basis of Sm2O3 or Eu2O3, respectively. Their purities were confirmed by powder XRD studies (Figure S2 in the Supporting Information). However, efforts to synthesize other compounds as pure phases have been made but were unsuccessful. The products of the hydrothermal reactions were very sensitive to the reaction conditions. Even when the same reaction conditions for compounds 2 and 3 were adopted to synthesize other rare-earth borate-sulfates, only rare-earth sulfates, such as RE2(SO4)3(H2O)n (n = 4 (P21/n), 5 (C2/c), 8 (C2/c)), or these rareearth sulfates with a small amount of rare-earth borate-sulfate crystals were obtained. Through hydrothermal syntheses under the reaction conditions given in Table S1, crystals of compounds 1, 4, 5, and 8−16 can be obtained but usually along with a large amount of rare-earth sulfates as impurities. Crystal Structure Determination. Single-crystal X-ray diffraction data collections were performed on an Agilent Technologies SuperNova Dual Wavelength CCD diffractometer with monochromated Mo Kα radiation (λ = 0.71073 Å) at room temperature. Data reductions were implemented using the program CrysAlisPro with a multiscan method applied for absorption correction.59 The structures were solved by using direct methods and refined on the basis of full-matrix least-squares fitting on F2 using SHELX-97.60 All non-hydrogen atoms were refined with anisotropic thermal parameters. On the basis of the requirement of charge balance and results of bond-valence calculations, the O atoms

corners in A3H(SO4)2(B2O3)2 (A = Rb, Cs). Obviously, the borate-sulfates exhibit rich structural chemistry. To further expand the metal borate-sulfate family, we focus on the explorations of rare-earth borate-sulfates. Rare-earth ions show flexible coordination geometries due to the so-called “lanthanide contraction”, which is favorable for the construction of novel structures. Lanthanide compounds also display unique luminescent and magnetic properties.49−57 Our systematic explorations in the RE−B−S−O system led to the discovery of 16 rare-earth borate-sulfates: namely, RE(SO4)[B(OH)4](H2O) (RE = La (1), Sm (2), Eu (3)), RE(SO4)[B(OH)4](H2O)2 (RE = Pr (4), Nd (5), Sm (6), Eu (7), Gd (8)), and RE(SO4)[B(OH)4](H2O)·H2O (RE = Tb (9), Dy (10), Ho (11), Er (12), Tm (13), Yb (14), Lu (15), Y (16)). They represent the first structurally characterized rare-earth borate-sulfate mixed-anion compounds. These compounds exhibit three different types of layered structures. Herein, the syntheses and crystal structures of these compounds are reported. Optical, thermal, and magnetic properties of compounds 2, 3, 6, and 7 are also presented.

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EXPERIMENTAL SECTION

Instruments and Characterization. X-ray diffraction (XRD) patterns of powder samples were collected on a Rigaku MiniFlex II diffractometer using monochromated Cu Kα radiation (λ = 1.5406 Å) with a step size of 0.02° at room temperature. Microprobe elemental analyses were performed on a field emission scanning electron microscope (FESEM, JSM6700F) equipped with energy dispersive Xray spectrometry (EDS, Oxford INCA). The UV−vis optical diffuse reflectance spectra were measured at room temperature on a PerkinElmer Lambda 950 UV−vis−NIR spectrophotometer with a BaSO4 plate used as a standard (100% reflectance). Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) were carried out simultaneously on a NETZSCH STA449C instrument at a heating rate of 5 °C min−1 under a flowing nitrogen atmosphere. Photoluminescence (PL) excitation and emission spectra, as well as PL decays, were obtained on an Edinburgh FLS920 fluorescence spectrometer equipped with both continuous (450 W) and pulsed xenon lamps. Temperature-dependent magnetic susceptibility measurements were carried out on a PPMS-9T magnetometer at 1000 Oe field from 2 to 300 K. Pascal’s constants were applied for the correction of the susceptibility of the container and the diamagnetic contributions of the samples.58 B

DOI: 10.1021/acs.inorgchem.7b02317 Inorg. Chem. XXXX, XXX, XXX−XXX

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Table 2. Crystallographic Data for RE(SO4)[B(OH)4](H2O)·H2O (RE = Tb (9), Dy (10), Ho (11), Er (12), Tm (13), Yb (14), Lu (15), Y (16)) RE(SO4)[B(OH)4](H2O)·H2O fw space group a (Å) b (Å) c (Å) α (deg) β (deg) γ (deg) V (Å3) Z ρcalcd (g cm−3) μ (mm−1) Rint GOF on F2 R1, wR2 (I > 2σ(I))a R1, wR2 (all data) a

RE = Tb (9)

RE = Dy (10)

RE = Ho (11)

RE = Er (12)

RE = Tm (13)

RE = Yb (14)

RE = Lu (15)

RE = Y (16)

369.87 P1̅ 6.0139(3) 6.8927(7) 10.1753(10) 79.616(8) 76.590(6) 89.106(6) 403.42(6) 2 3.045 6.761 0.0505 1.075 0.0297, 0.0523 0.0370, 0.0557

373.43 P1̅ 5.9880(3) 6.8728(6) 10.1638(8) 79.652(7) 76.597(6) 89.153(6) 400.12(5) 2 3.100 9.632 0.0517 1.070 0.0278, 0.0552 0.0335, 0.0585

375.86 P1̅ 5.9701(3) 6.8570(5) 10.1580(7) 79.588(6) 76.636(5) 89.193(5) 397.75(4) 2 3.138 10.242 0.0531 1.033 0.0278, 0.0562 0.0328, 0.0587

378.19 P1̅ 5.9529(3) 6.8401(5) 10.1553(7) 79.598(6) 76.642(6) 89.198(6) 395.54(4) 2 3.175 10.906 0.0547 1.053 0.0266, 0.0529 0.0308, 0.0550

379.86 P1̅ 5.9289(3) 6.8232(5) 10.1422(8) 79.531(6) 76.663(6) 89.263(5) 392.40(5) 2 3.215 11.605 0.0659 1.060 0.0311, 0.0742 0.0336, 0.0763

383.97 P1̅ 5.9150(2) 6.8090(5) 10.1454(8) 79.541(6) 76.669(5) 89.243(4) 390.82(4) 2 3.263 12.266 0.0394 1.038 0.0210, 0.0467 0.0227, 0.0477

385.91 P1̅ 5.8992(2) 6.7954(4) 10.1322(5) 79.551(5) 76.691(4) 89.266(4) 388.53(3) 2 3.299 13.007 0.0339 1.064 0.0193, 0.0456 0.0205, 0.0463

299.85 P1̅ 5.9679(3) 6.8559(4) 10.1698(7) 79.608(5) 76.637(5) 89.220(4) 398.02(4) 2 2.502 7.622 0.0446 1.055 0.0267, 0.0596 0.0306, 0.0615

R1 = ∑||Fo| − |Fc||/∑|Fo|; wR2 = {∑w[(Fo)2 − (Fc)2]2/∑w[(Fo)2]2}1/2.

Figure 1. Coordination geometry around the Eu3+ ion (a), the 1D ladderlike europium sulfate chain along the b axis (b), the 1D europium borate chain along the a axis (c), the double layer of Eu(SO4)[B(OH)4] parallel to the ab plane (d), and view of the structure of Eu(SO4)[B(OH)4](H2O) down the a axis (e). linked with B atoms were all assigned to hydroxyl groups. All hydrogen atoms were located at geometrically calculated positions and refined with isotropic thermal parameters. The crystallographic data are summarized in Tables 1 and 2, and selected bond lengths and angles are given in Tables S2−S4 in the Supporting Information. More details of the crystal structure investigations can be obtained from the Cambridge Crystallographic Data Centre (CCDC) on quoting the depository numbers CCDC 1573387−1573402 (Web site http://www. ccdc.cam.ac.uk), as well as from the Inorganic Crystal Structure

Database (ICSD) with numbers CSD 433550−433565 (Web site http://www.fiz-karlsruhe.de and e-mail crysdata@fiz-karlsruhe.de).

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RESULTS AND DISCUSSION Hydrothermal reactions of rare-earth oxides, H3BO3, and H2SO4 afforded 16 new hydrated rare-earth borate-sulfate mixed-anion compounds: namely, RE(SO4)[B(OH)4](H2O) (RE = La (1), Sm (2), Eu (3)), RE(SO4)[B(OH)4](H2O)2 (RE = Pr (4), Nd C

DOI: 10.1021/acs.inorgchem.7b02317 Inorg. Chem. XXXX, XXX, XXX−XXX

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Figure 2. Coordination geometry around the Eu3+ ion (a), the 1D europium sulfate chain along the c axis (b), the 1D europium borate chain along the a axis (c), the simple layer of Eu(SO4)[B(OH)4] parallel to the ac plane (d), and view of the structure of Eu(SO4)[B(OH)4](H2O)2 down the c axis (e).

(5), Sm (6), Eu (7), Gd (8)), and RE(SO4)[B(OH)4](H2O)· H2O (RE = Tb (9), Dy (10), Ho (11), Er (12), Tm (13), Yb (14), Lu (15), Y (16)). Although their chemical compositions exhibit small differences, these compounds feature three different types of layered structures. Via hydrothermal reactions of the same starting materials but under different synthetic conditions including reaction temperatures and molar ratios of the reactants, single phases of two Sm compounds (2 and 6) as well as two Eu compounds (3 and 7) can be isolated (Table S1 in the Supporting Information). It is found that, in comparison with compounds 6 and 7, the syntheses of compounds 2 and 3 require a larger amount of H3BO3 and higher reaction temperature. The thermal stability, UV−vis optical diffuse reflectance spectra, and luminescent and magnetic properties of these four compounds have been studied. Structural Description. RE(SO4)[B(OH)4](H2O) (RE = La (1), Sm (2), Eu (3)) are isostructural and crystallize in the space group P1̅. Their structures feature a double-layered structure in which the rare-earth-metal ions are bridged by BO4 and SO4 groups (Figure 1). The structure of 3 will be discussed in detail as a representative. Its asymmetric unit consists of 12 non-hydrogen atoms: 1 Eu, 1 B, 1 S, and 9 O atoms, all of which are located at the general sites. Among the nine unique O atoms, O(5), O(6), O(7), and O(8) are all singly protonated, and O(1W) is an aqua ligand. B(1) is tetrahedrally coordinated by O(5), O(6), O(7), and O(8), forming a B(OH)4 unit. The B−O bond distances and O−B−O bond angles are in the ranges of 1.457(6)−1.468(6) Å and 99.6(4)−114.8(4)°, respectively (Table S2 in the Supporting Information). The S(1)

atom is coordinated by O(1), O(2), O(3), and O(4), in a regular tetrahedral geometry with S−O distances and O−S−O angles in the normal ranges of 1.453(3)−1.492(3) Å and 104.0(2)− 111.9(2)°, respectively (Table S2). These bond distances are close to those reported in borosulfates.37−39 The Eu(1) atom is nine-coordinated by two borate and one sulfate anions in a bidentate chelating fashion, two other sulfate anions in a unidentate fashion, and an aqua ligand (Figure 1a). Its coordination geometry can be described as a tricapped trigonal prism. The Eu−O distances are in the range of 2.371(3)− 2.645(4) Å (Table S2). The interconnection of Eu3+ ions by chelating and bridging sulfate groups led to a ladderlike europium(III) sulfate chain along the b axis with Eu2O2 four-membered rings and Eu2S2O4 eight-membered rings, whereas the interconnection of Eu3+ ions by chelating and bridging borate groups led to a 1D europium(III) borate chain along the a axis (Figure 1b,c). The sulfate anion is tetradentate, and it chelates with a Eu3+ ion bidentately and also bridges with two other Eu3+ ions, O(2) remains noncoordinated, and the borate group is also tetradentate and forms two four-membered chelating rings with two Eu3+ ions (Figure 1c). These two types of 1D chains are further interconnected into a 2D europium borate-sulfate double layer in the ab plane (Figure 1d), and the aqua ligands which occupy the vacant coordination sites of the rare-earth ions are orientated toward the interlayer space (Figure 1e). There exist a few hydrogen bonds among the aqua ligands, OH groups of the borate anions, and noncoordinated sulfate oxygen atoms (Table D

DOI: 10.1021/acs.inorgchem.7b02317 Inorg. Chem. XXXX, XXX, XXX−XXX

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Figure 3. Coordination geometry around the Lu3+ ion (a), the 1D ladderlike lutetium sulfate chain along the b axis (b), the 1D lutetium borate chain along the a axis (c), the double layer of Lu(SO4)[B(OH)4] parallel to the ab plane (d), and view of the structure of Lu(SO4)[B(OH)4](H2O)·H2O down the a axis (e).

2.381(3)−2.586(4) Å (Table S3). These B−O, S−O, and Eu−O distances are close to those in 3. Different from that in 3, the interconnection of Eu3+ ions by the sulfate anions led to a simple chain along the c axis (Figure 2b). Each sulfate anion is tridentate; it forms a four-membered chelating ring with a Eu3+ ion and also bridges with one other Eu3+ ion, and O(2) remains noncoordinated. Such a coordination mode is different from that in 3. These 1D lanthanide sulfate chains are further interconnected by borate groups into a layered architecture (Figure 2d). The coordination mode of the borate anion is same as that in 3, as is the Eu−borate chain formed (Figure 2c). The aqua ligands are also orientated toward the interlayer space, and they satisfy the coordination number required by the Eu3+ ion (Figure 2e). The 2D structure is further stabilized by extensive hydrogen bonds formed among aqua ligands and sulfate and borate anions (Table S5 in the Supporting Information). It is believed that the different layered structures formed between compounds 3 and 7 are mainly due to the different numbers of aqua ligands present in the coordination sphere of the Eu3+ ion and the different coordination modes the sulfate anions adopted. RE(SO4)[B(OH)4](H2O)·H2O (RE = Tb (9), Dy (10), Ho (11), Er (12), Tm (13), Yb (14), Lu (15), Y (16)) are isostructural and crystallize in the space group P1̅. Their structures feature another type of double-layered structure composed of RE3+ ions bridged by BO4 and SO4 tetrahedra (Figure 3). The structure of 15 will be described in detail as a

S5 in the Supporting Information), which provides further stabilization for the structure. RE(SO4)[B(OH)4](H2O)2 (RE = Pr (4), Nd (5), Sm (6), Eu (7), Gd (8)) are isostructural and crystallize in the space group P21/m. Their structures feature a single 2D layer in which the lanthanide ions are bridged by BO4 and SO4 tetrahedra (Figure 2). Here only the structure of 7 will be discussed exhaustively as a representative. The asymmetric unit of 7 consists of 10 nonhydrogen atoms: 1 Eu, 1 B, 1 S, and 7 O atoms. The Eu(1), B(1), S(1), O(1), O(2), O(4), and O(5) atoms sit on the mirror planes, whereas the other atoms are located at the general sites. Among these 7 O atoms, O(4), O(5), and O(6) are singly protonated, and O(1W) corresponds to an aqua ligand. B(1) is tetrahedrally coordinated by four hydroxyl groups of O(4), O(5), and two O(6) atoms, forming a B(OH)4 unit like that in 3. The B−O bond distances and O−B−O bond angles are in the ranges of 1.445(6)−1.459(1) Å and 98.9(5)−115.0(4)°, respectively (Table S3 in the Supporting Information). The S(1) atom is coordinated by O(1), O(2), and two O(3) atoms in a regular SO4 tetrahedral geometry with S−O distances and O−S−O angles in the ranges of 1.455(5)−1.471(4) Å and 104.6(3)−112.0(3)°, respectively (Table S3). The Eu(1) atom is nine-coordinated by nine oxygen atoms from one sulfate and two borate anions in a bidentate chelating mode, one sulfate anion in a unidentate fashion, and two aqua ligands, forming a EuO9 tricapped trigonal prism (Figure 2a); the Eu−O distances are in the range of E

DOI: 10.1021/acs.inorgchem.7b02317 Inorg. Chem. XXXX, XXX, XXX−XXX

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Figure 4. TGA and DSC curves of compounds 2 (a), 3 (b), 6 (c), and 7 (d).

vacant coordination sites of the rare-earth ions are oriented toward the interlayer space, as are the lattice water molecules (Figure 3e). There are hydrogen bonds among the lattice water molecules, the aqua ligands, the OH groups of the borate anions and noncoordinated sulfate oxygen atoms (Table S5 in the Supporting Information), which provide further stabilization of the structure. The different double-layered structure in compound 15 in comparison to that in compound 3 is mainly due to the lower coordination number for the Lu3+ ion in comparison with that of Eu3+ and the different coordination mode adopted by the sulfate anions (no chelation ring is formed in compound 15). It is worth pointing out that the chemical compositions of the three types of compounds exhibit very small difference. In comparison with RE(SO4)[B(OH)4](H2O) (1−3), both RE(SO4)[B(OH)4](H2O)2 (4−8) and RE(SO4)[B(OH)4](H2O)·H2O (9−16) contain one more water molecule per formula unit. The water molecules in RE(SO4)[B(OH)4](H2O) (1−3) and RE(SO4)[B(OH)4](H2O)2 (4−8) are bonded with the rare earth ions whereas RE(SO4)[B(OH)4](H2O)·H2O (9− 16) contain additional lattice water molecules. These water molecules act as interlayer spacers and provide hydrogen bonds to stabilize the structure (Table S5 in the Supporting Information). These differences play an important role in the construction of these three different types of layered structures. Furthermore, the “lanthanide contraction” also works in the structural diversity. Within all of these three types of compounds

representative. The asymmetric unit of compound 15 contains 13 unique non-hydrogen atoms: 1 Lu, 1 B, 1 S and 10 O atoms, all of which are located at the general sites. Among these 10 unique O atoms, O(5), O(6), O(7), and O(8) are singly protonated, while O(1W) and O(2W) correspond to water molecules. S(1) and B(1) atoms are four-coordinated by four oxygen atoms and four hydroxyl groups, respectively, which is similar to the case for the above two types of structures. The Lu(1) atom is eightcoordinated by two borates in a bidentate chelating fashion, three sulfate anions in a unidentate fashion, and an aqua ligand (Figure 3a). The B−O and S−O bond lengths and corresponding bond angles are close to those in the structures of compounds 3 and 7 (Table S4 in the Supporting Information). The Lu−O distances fall in the range of 2.219(4)−2.382(4) Å (Table S4), which are slightly shorter than the Eu−O bonds in compounds 3 and 7. The interconnection of Lu3+ ions by bridging sulfate groups led to another type of ladderlike lutetium(III) sulfate chain along the b axis with uniform Lu2S2O4 eight-membered rings (Figure 3b). The sulfate anion is tridentate; it bridges with three Lu3+ ions through three oxygen atoms and the fourth oxygen atom O(3) remains noncoordinated. The coordination mode of the borate group and the lutetium borate chain are similar to those in compounds 3 and 7 (Figure 3c). The 1D chains of lutetium sulfate and lutetium borate are further interconnected by sharing Lu3+ ions into a lutetium borate-sulfate double layer in the ab plane, showing uniform 1D tunnels of four-membered rings along the a axis (Figure 3d). The aqua ligands which occupy the F

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Figure 5. UV/vis diffuse reflectance spectra of compounds 2 (a), 3 (b), 6 (c), and 7 (d). The absorption peaks are marked with red asterisks.

(except the Y3+ compound), the RE−O bond lengths decrease with increasing atomic number. For the isostructural compounds, the unit cell parameters also change with the “lanthanide contraction”. The cell volume constricts by 3.9% from compounds 4 to 8 and by 1.3% from compounds 9 to 16. The coordination numbers of RE3+ ions also change with a decrease in the ionic radii. In these compounds, nine-coordination is preferred by the light and middle lanthanide metals, whereas the heavy lanthanide ions show a lower coordination number of 8. Due to the “lanthanide contraction” effect and the different numbers of aqua ligands in the coordination sphere of RE3+ ions, the numbers of sulfate anions coordinated to the RE3+ ions and their coordination modes are quite different (Figures 1a−3a). As there are two aqua ligands bonded to one RE3+ ion in compounds 4−8, one more than in compounds 1−3 and 9−16, there are three sulfate anions coordinated to one RE3+ ion in 1−3 and 9− 16, while there are only two in 4−8. Furthermore, corresponding to the “lanthanide contraction”, all sulfate anions coordinate to the RE3+ ion in a unidentate fashion in compounds 9−16, but in addition to the unidentate fashion, the bidentate chelating mode is also adopted by sulfate anions to coordinate to the RE3+ ion in compounds 1−3 and 4−8. Such different coordination environments of rare-earth ions further result in the formation of varying rare-earth sulfate chains (Figures 1b−3b). Interestingly, the RE− S−O double chains in 1−3 and 9−16 can be viewed as being derived from the RE−S−O single chains in 4−8. One rare-earth sulfate double chain in 1−3 is formed by two RE−S−O single chains (Figure 1b), and such single chains are same as those in

4−8 (Figure 2b). These two single chains are bridged by the RE− O bonds perpendicular to the chains into the double chains, and formation of such RE−O bonds is due to the one additional sulfate anion coordinated to the RE3+ ion in 1−3 in comparison to that in 4−8. The rare-earth sulfate double chain in 9−16 can also be viewed as being formed by two simple RE−S−O single chains, but such RE−S−O single chains are different from those in 4−8 (Figures 2b and 3b). As three sulfate anions are coordinated to the RE3+ ion in 9−16, the small four-membered RESO2 chelate rings within the single chain in 4−8 are broken, and then the large eight-membered RE2S2O4 rings between two single chains were formed, which led to the formation of double rare-earth sulfate chains in 9−16. Finally, such different rareearth sulfate chains are bridged by the borate groups into three types of layered structures. Because the rare-earth borate chains are the same in all types of structures, the double-layered structures in 1−3 and 9−16 originate from the single-layer structure in 4−8 along the similar evolution paths of the RE−S− O chains. It is worth noting that these 16 new rare earth compounds greatly enrich the metal borate-sulfate family. As we mentioned above, reports on metal borate-sulfates are very limited, and only seven compounds have been structurally characterized. Therefore, metal borate-sulfates are almost a pristine area. Here the presenting rare earth compounds exhibit interesting structural variability, implying that the combination of sulfate and borate can construct mixed-anion compounds with various novel structures. Hence, borate-sulfate mixed-anion compounds G

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Figure 6. Solid-state emission spectra of compounds 2 and 6 (a) and compounds 3 and 7 (b).

Luminescent Properties. Solid-state luminescent spectra of compounds 2, 3, 6, and 7 have been studied at room temperature. Consistent with the UV−vis diffuse reflectance spectra, the excitation spectra exhibit an excitation maximum at 402 nm for Sm-containing compounds and 395 nm for Eu-containing compounds (Figure S4 in the Supporting Information), due to the large oscillation strength of Sm3+ 6H5/2 → 4F7/2 and Eu3+ 7F0 → 5L6 transitions. Figure 6a shows the emission spectra of compounds 2 and 6. Under 402 nm excitation, compounds 2 and 6 exhibit four groups of emission peaks originating from the 4G5/2 → 6HJ transition of Sm3+ ions: 4G5/2 → 6H5/2 (550−570 nm), 4G5/2 → 6 H7/2 (580−610 nm), 4G5/2 → 6H9/2 (630−660 nm), and 4G5/2 → 6H11/2 (690−720 nm).66−70 At 402 nm, Sm3+ ions are excited to the high-lying 4F7/2 state, and then they would quickly relax nonradiatively from the 4F7/2 state to the metastable 4G5/2 state. The presence of a series of states with a slight energy difference between 4F7/2 and 4G5/2 states promotes the nonradiative relaxation, which leads to the population of the 4G5/2 state. Due to the large energy gap between 4G5/2 and the low-lying 6HJ states, the metastable 4G5/2 state can remain for a long time, and luminescence is emitted. The four emission bands all consisted of several split emission peaks due to the energy level splitting by the crystal field, which indicates a well-ordered lattice site occupation for Sm3+ ions in compounds 2 and 6. The three most intense emission peaks are located at 594 (orange), 602 (orange), and 642 nm (orange-red) for both compounds 2 and 6, corresponding to useful light in color displays and optical storage applications.71,72 The 4G5/2 lifetimes of Sm3+ are less than 1 μs for both compounds 2 and 6. Figure 6b shows the emission spectra of compounds 3 and 7 measured under excitation at 395 nm. Both compounds display four emission bands at about 580−600, 605−630, 645−660, and 680−710 nm, which can be assigned to the Eu3+ transitions of 5 D0 → 7FJ with J = 1−4, respectively.66−70 Similarly to the transition processes of Sm3+ ions, the Eu3+ ions should be excited to the high-lying 5L6 state by 395 nm light and then relax to 5D0 by nonradiative followed by radiative transitions of 5D0 → 7FJ. Due to the low local symmetry taken by Eu3+ in the structures of compounds 3 and 7, each emission band is composed of several well-resolved peaks, corresponding to the splitting of 7FJ energy

should be a promising system for studying structural chemistry and exploring functional materials. Thermal Analyses. Thermogravimetric analysis (TGA) studies reveal that compounds 2 and 3 are both thermally stable up to about 200 °C, whereas compounds 6 and 7 are thermally stable up to about 140 °C (Figure 4). Upon further heating, TGA diagrams display continuous weight losses until 500 °C for all compounds, which should be attributed to the removal of crystalline water and the dehydration of hydroxyl groups of the borate anions. The observed total weight losses of 15.5%, 15.3%, 20.0%, and 19.1%, are very close to the calculated values of 15.7%, 15.7%, 19.9%, and 19.8%, for compounds 2, 3, 6, and 7, respectively. The differential scanning calorimetry (DSC) curves of compounds 2, 3, 6, and 7 exhibit strong endothermic peaks at 266, 262, 195, and 199 °C, respectively, which further confirm the dehydration of these compounds. Furthermore, samples of 3 and 6 have been heated at 300 °C for 2 h. On the basis of the powder XRD studies, the residues were determined to be amorphous phases for compound 3 and unidentified phases for compound 6 (Figure S3 in the Supporting Information). Powder XRD patterns of these residues are both completely different from the patterns of 3 and 6 crystals, which also implies that dehydration reactions occurred. UV−Vis Diffuse Reflectance Spectra. As shown in Figure 5, the UV−vis diffuse reflectance spectra indicate that the shortwavelength absorption edges extend to the UV range for compounds 2, 3, 6, and 7. On the basis of the absorption (α/S) data calculated from the reflectance spectra using the Kubelka− Munk function, the optical band gaps are estimated to be 4.66 eV (266 nm), 4.53 eV (274 nm), 4.62 eV (268 nm), and 4.50 eV (276 nm) for compounds 2, 3, 6, and 7, respectively. Furthermore, the diffuse reflectance spectra exhibit a series of narrow absorption peaks located at around 305, 318, 345, 362, 375, 390, 402, 416, 438, 462, 478, 499, 560 nm for both Smcontaining compounds (2 and 6) and 285, 298, 317, 362, 376, 385, 395, 415, 465, 526, 534, and 589 nm for both Eu-containing compounds (3 and 7), which can be assigned to the 4f−4f inner shell electronic transitions of Sm3+ and Eu3+ ions, respectively.61−65 The most intense absorption peak centered at 402 nm for compounds 2 and 6 originates from the Sm3+ 6H5/2−4F7/2 transition, and that at 395 nm for compounds 3 and 7 originates from the Eu3+ 7F0−5L6 transition.62−65 H

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Figure 7. Plots of χmol vs T and χmol−1 vs T of compounds 2 (a), 3 (b), 6 (c), and 7 (d).

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levels of Eu3+. All the transitions of 5D0 → 7F1,2,4 exhibit relatively high intensity for both compounds, and the strongest emission peaks are located at 695 nm (red) and 588 (orange) for compounds 3 and 7, respectively. The lifetimes of the Eu (5D0) state are measured to be about 0.215 ms for compound 3 and 0.190 ms for compound 7. Magnetic Properties. The magnetic susceptibilities for compounds 2, 3, 6, and 7 have been measured in the temperature range of 2−300 K with an applied magnetic field of 1000 Oe. Figure 7 shows the temperature dependence of molar magnetic susceptibility (χmol) and corresponding reciprocal susceptibility (χmol−1). For all compounds, the values of molar magnetic susceptibility (χmol) increase with a decrease in temperature, but the temperature dependence of χmol−1 for all compounds seriously deviates from the Curie−Weiss law, which is due to the closeness in energy between some excited states and ground states for Eu3+ and Sm3+ ions.73 At 300 K, the effective magnetic moments, μeff, are calculated to be 1.40, 3.29, 1.46, and 3.25 μB for compounds 2, 3, 6, and 7, respectively. These values are close to the corresponding theoretical values of 1.55−1.65 and 3.40−3.51 μB for the Sm3+ and Eu3+ ions, respectively.73 As shown in Figure S5 in the Supporting Information, the χmolT value decreases continuously with cooling and the μeff values reach 0.60, 0.34, 0.57, and 0.33 μB at 2 K for compounds 2, 3, 6, and 7, respectively, which suggests the existence of antiferromagnetic interactions between the magnetic centers (Sm3+ or Eu3+) in these compounds.73−75

CONCLUSIONS In summary, the first rare-earth borate-sulfate mixed-anion compounds have been synthesized using the hydrothermal method. They possess the same fundamental building anionic units of SO4 and B(OH)4 tetrahedra but feature three different types of layered structures. These 2D layers are further interconnected by extensive hydrogen bonds associated with sulfate anions, borate groups, aqua ligands, and lattice water molecules. The different layered structures formed are due to the different coordination numbers for the rare-earth ions and the different numbers of aqua ligands as well as the various coordination modes the sulfate anions adopted. These 16 new rare-earth compounds greatly enrich the metal borate-sulfate family, and the interesting structural variability implies that the combination of sulfate and borate can construct mixed-anion compounds with novel structures. Luminescent studies show that compounds 2, 3, 6, and 7 emit intense light in the orange or red region. It is expected that many other lanthanide boratesulfates can be obtained by changing the Ln/B/S molar ratios and pH values of reaction media, and studies on these possibilities are underway in our laboratory.

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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.7b02317. I

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Powder X-ray diffraction patterns, EDS results, solid-state excitation spectra, compositions of the starting materials for the hydrothermal syntheses, bond lengths and angles, and hydrogen bonds (PDF) Accession Codes

CCDC 1573387−1573402 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 Authors

*E-mail for X.X.: [email protected]. *E-mail for J.-G.M: [email protected]. ORCID

Xiang Xu: 0000-0003-4132-5322 Jiang-Gao Mao: 0000-0002-5101-8898 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by National Natural Science Foundation of China (Grant Nos. 21401194, 21373222, 21231006, 91622112) and the Strategic Priority Research Program of the Chinese Academy of Sciences (Grant No. XDB20000000).

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DOI: 10.1021/acs.inorgchem.7b02317 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry (75) Yang, H.; Hu, C.-L.; Mao, J.-G. Ln2Ga[B3O6(OH)]2[B7O9(OH)2](CH3CO2)2 (Ln = Y, Sm, Eu, Gd, Dy): A Series of Lanthanide Galloborates Decorated by Acetate Anions. Inorg. Chem. 2016, 55, 6051−6060.

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DOI: 10.1021/acs.inorgchem.7b02317 Inorg. Chem. XXXX, XXX, XXX−XXX