LnBSb2O8 (Ln = Sm, Eu, Gd, Tb): A Series of Lanthanide

Sep 30, 2016 - A series of lanthanide boroantimonates, namely, LnBSb2O8 (Ln = Sm 1, Eu 2, Gd 3, and Tb 4) have been successfully synthesized by high ...
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LnBSb2O8 (Ln = Sm, Eu, Gd, Tb): A Series of Lanthanide Boroantimonates with Unusual 3D Anionic Structures Dong Yan,†,‡ Fei-Fei Mao,†,‡ 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, P. R. China ‡ University of the Chinese Academy of Sciences, Beijing 100039, P. R. China S Supporting Information *

ABSTRACT: A series of lanthanide boroantimonates, namely, LnBSb2O8 (Ln = Sm 1, Eu 2, Gd 3, and Tb 4) have been successfully synthesized by high temperature solid-state reactions for the first time. They are isostructural and feature novel three-dimensional (3D) frameworks composed of 2D [Sb3O12]9− layers interconnected by 1D [SbBO7]6− chains with remaining BO3 groups hanging on the walls of the 1D 6-membered-ring (MR) tunnels along the a-axis, and the lanthanide ions filled in the voids of the anionic structure. They exhibit high thermal stability (up to 900 °C). Luminescent studies suggest that compounds 1, 2, and 4 have potential application as orange, red, and green light luminescent materials, respectively. Magnetic measurements reveal ferromagnetic coupling interactions in compound 3 and antiferromagnetic coupling interactions between magnetic centers in compounds 1, 2, and 4.

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INTRODUCTION Abundant research attention has been devoted to metal borates due to their numerous structural types and important applications as second-order nonlinear optical (NLO), birefringent, and luminescent materials.1−5 From the structural point of view, boron can form with oxygen atoms into a BO3 planar triangle or a BO4 tetrahedron, which can be further interlinked by corner-sharing or edgesharing into various fundamental building blocks (FBBs), from [B2O5]4− to [B18O36]18−.6−9 It has been confirmed that the connection of B−O groups with heteroatoms was a promising method to enrich the family of borates. A host of oxo anions of the post-transition metal elements have been introduced into borates, which led to the isolations of various borogermanates,10 borophosphates,11 borosulfates,12 and boroselenites,13 etc. By the combination of selenite and borate groups, a variety of boroselenites, including Se2B2O7,13a K2Se2B2O7,13b ASeB3O7 (A = Na, K),13b and Li2SeB8O15,13b have been obtained, among which Se2B2O713a shows a moderate SHG signal. The integration of the GeO4 tetrahedra with various borate groups has afforded a series of metal borogermanates,10 such as KBGe2O6,10c K2[GeB4O9]·2H2O,10b and CsB3GeO7.10a It is known that antimony exhibits two different oxidation states (+3 and +5),14 with Sb(III) intending to form an asymmetric SbIIIO3 trigonal pyramid whereas Sb(V) exhibits SbVO6 octahedral coordination geometry.14 These SbOn polyhedra can be further interlinked via Sb−O−Sb bridges into various types of extended frameworks. Thus, the combination of borate groups with the SbOn polyhedra is expected to produce a host of novel borates which have interesting structures and excellent © XXXX American Chemical Society

physical properties. But up to the present, reports on boroantimonites and boroantimonates are still limited.15 The boroantimonates reported include K3Sb4BO13,15c KSbB2O6,15a BaSb 2 B 4 O 1 2 , 1 5 a KSbOB 2 O 5 , 1 5 b α-RbSbOB 2 O 5 , 1 5 d βRbSbB2O6,15e and A2SbB3O8 (A = Na, K, Rb).15e KSbB2O6 and BaSb2B4O12 exhibit two kinds of 3D frameworks consisting of 1D SbO6 octahedral chains which are interconnected via B2O5 groups. A2SbB3O8 (A = Na, K, Rb) features a 3D anionic network composed of B3O8 groups and SbO6 octahedra with 1D tunnels of Sb4B4 8-membered-rings (MRs) along the a-axis. K3BSb4O13 features a novel 3D network built by (Sb3O9)n layers alternatively interconnected couples of SbO6 octahedra via edge-sharing and BO3 triangles along the c direction, forming tunnels along both a and b directions, which are filled with K+ ions. From the above discussions, it can be noticed that changing the ratio of B/Sb can produce different structures. With the increase of the B/Sb ratio, SbO6 octahedra would not be interconnected but form Sb−O−B bridges; when the B/Sb ratio is reduced, the SbO6 octahedra can be interconnected with each other to form a novel 3D anionic network. To the best of our knowledge, no lanthanide boroantimonates have been reported. In the field of fluorescence and laser application, lanthanide ions play a significant role due to their unusual spectral characters.16 Because of various coordination modes, hyperpolarizability from the distorted lanthanides oxide polyhedron, and interesting magnetic properties, lanthanides are very important in material chemistry of borates crystals. Received: July 25, 2016

A

DOI: 10.1021/acs.inorgchem.6b01790 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry Table 1. Summary of Crystal Data and Structural Refinements for Title Four Compounds Formula Fw crystal system space group a/Å b/Å c/Å V/Å3 Z Dc(g·cm−3) μ(Mo Kα) (mm−1) GOF on F2 R1, wR2 [I > 2σ(I)]a R1, wR2 (all data) a

SmSb2BO8 532.66

EuSb2BO8

GdSb2BO8

534.27

TbSb2BO8

539.56

541.23

12.5730(5) 7.2605(3) 12.6920(5) 1158.61(8)

12.5594(8) 7.2369(4) 12.6913(9) 1153.53(13)

12.532(4) 7.236(2) 12.671(4) 1149.0(6)

6.126 19.960 1.088 0.0308, 0.0616 0.0350, 0.0632

6.214 20.672 1.050 0.0261, 0.0561 0.0307, 0.0588

6.257 21.518 1.125 0.0281, 0.0573 0.0329, 0.0598

orthorhombic Pnma (No.62) 12.6155(7) 7.2702(4) 12.7086(7) 1165.60(11) 8 6.071 19.154 1.196 0.0681,0.1510 0.0743,0.1541

R1 = ∑∥Fo| − |Fc∥/∑|Fo|, wR2 = {∑w[(Fo)2 − (Fc)2]2/∑w[(Fo)2]2}1/2. grinding steps and then cooling to 30 °C at a rate of 5 °C/h. PXRD studies were used to confirm the purity of these polycrystalline samples (Figure S1). IR data (Figure S4) (KBr cm−1): 1487(m), 1383(m), 1150(m), 980(w), 747(s), 638(w), 467(s) for SmSb2BO8; 1481(m), 1385(m), 1156(m), 987(w), 756(s), 636(w), 471(s) for EuSb2BO8; 1489(m), 1385(m), 1149(m), 979(w), 756(s), 632(w), 474(s) for GdSb2BO8; 1492(m), 1383(m), 1144(m), 986(w), 774(s), 631(w), 490(s) for TbSb2BO8. Single Crystal Structure Determinations. Single crystal diffraction data for LnBSb2O8 (Ln = Sm 1, Eu 2, Gd 3, Tb 4) were collected by using SuperNova X-ray Source, Mo Kα/Cu radiation at 298 K. The Lorentz and polarization factors and Multiscan method were used to correct all four data sets and absorption, respectively.18 All four structures were solved by direct methods and refined by a full−matrix least−squares fitting on F2 by SHELX-97.19 The program PLATON was used to check possible missing symmetry for all four structures, but none was found.20 Crystal data and the structural refinements information on all four compounds are reported in Table 1. Important bond distances are given in Table 2. Further details on the crystal studies are supplied in the Supporting Information.

Our exploration of novel compounds in the Ln(III)−Sb(V)− B(III)−O system resulted in the isolation of the first examples of lanthanide boroantimonates, namely, LnBSb2O8 (Ln = Sm 1, Eu 2, Gd 3, and Tb 4). Herein, their syntheses, crystal structures, luminescent and magnetic properties are presented.

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EXPERIMENTAL SECTION

Materials and Methods. Reagents were obtained as follows: Sm2O3 (Aladdin, 99.8%), Eu2O3 (Aladdin, 99.8%), Gd2O3 (Aladdin, 99.8%), Tb4O7 (Aladdin, 99.8%), Sb2O3 (Zheng’an Chemical Factory, ≥ 98.0%), Sb2O5 (Zheng’an Chemical Factory, 99.98%), and H3BO3 (Aladdin, 99.8%). A field emission scanning electron microscope (FESEM, JSM6700F) equipped with an energy dispersive X-ray spectroscope (EDS, Oxford INCA) was used to perform the microprobe elemental analyses. X-ray powder diffraction (XRD) patterns were collected on a Panalytical X’pert Pro MPD diffractometer using graphite-monochromated Cu Kα radiation in the 2θ range of 5−75° with a step size of 0.02°. IR spectra were recorded on a Magna 750 FT-IR spectrometer as KBr pellets in the range 4000−400 cm−1. A PE Lambda 900 UV−vis spectrophotometer was used to measure the optical diffuse reflectance spectra at room temperature. A BaSO4 plate was used as a standard (100% reflectance). The Kubelka−Munk function, α/S = (1 − R)2/2R,17 was used to calculate the absorption spectrum from the reflectance spectrum, where α is the absorption coefficient, S is the scattering coefficient, which is practically wavelength independent when the particle size is larger than 5 μm, and R is the reflectance. NETZSCH STA 449C units were used to carry out the thermogravimetric analyses with a heating rate of 10 °C/min under N2 atmosphere. Room-temperature photoluminescence studies and the relevant lifetime decay curves were accomplished on an Edinburgh FLS920 and FSP920 fluorescence spectrometer. A PPMS-9T magnetometer was used to accomplish the magnetic susceptibility tests in the range of 2−300 K at 1000 Oe field. Preparation of LnBSb2O8 (Ln = Sm 1, Eu 2, Gd 3, Tb 4). The traditional high temperature solid-state method was used to obtain the single crystals of title compounds. The reaction mixtures composed of Ln2O3 (0.15 mmol) (Ln = Sm, Eu, Gd) or Tb4O7 (0.075 mmol), Sb2O3 (0.1457g, 0.5 mmol), and H3BO3 (0.2480g, 4 mmol) were ground fully before being transferred into platinum crucibles. The mixtures were heated at 950 °C for 72 h, and then cooled to 750 °C at a rate of 5 °C/h, followed by cooling to 500 °C at a rate of 50 °C/h. The average atomic ratios of Ln/Sb (Ln = Sm 1, Eu 2, Gd 3, Tb 4) recorded by energy-dispersive spectrometry (EDS) on several crystals of 1−4 are 2.06:1, 2.13:1, 2.07:1, and 2.09:1, respectively, which are close to those from single crystal X-ray structural analyses. The polycrystalline samples of LnBSb2O8 (Ln = Sm, Eu, Gd, Tb) were obtained by the reactions of Ln2O3 (Ln = Sm, Eu, Gd) (0.5 mmol) or Tb4O7 (0.25 mmol), Sb2O5 (1.0 mmol), and H3BO3 (3.0 mmol) in a molar ratio of 1:2:6 at 920 °C for 72 h with several intermittent

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RESULTS AND DISCUSSION Structure of LnBSb2O8 (Ln = Sm 1, Eu 2, Gd 3, Tb 4). LnBSb2O8 (Ln = Sm 1, Eu 2, Gd 3, Tb 4) crystallize in centrosymmetric space group Pnma. As all four compounds are isostructural and display similar 3D structure, only the structure of EuSb2BO8 will be described in detail as a representation. EuSb2BO8 exhibits a novel crystal structure, which embodies a complicated 3D anionic framework composed of 2D [Sb3O12]9− layers interconnected by 1D [SbBO7]6− chains with B(1)O3 groups hanging on the walls of the 1D tunnels of Sb6 six-member rings (MRs) (Figure 1). The asymmetric unit of EuBSb2O8 contains two Eu, four Sb, two B, and 12 O atoms, among which Eu(1), Eu(2), Sb(1), Sb(3), B(1), B(2), O(1), O(2), O(3), O(4), O(5), O(6), O(9), and O(12) are located on mirror planes, Sb(2) and Sb(4) at the inversion center, and O(7), O(8), O(10), and O(11) at general sites. All four Sb atoms have coordination modes with six oxygen atoms. The Sb−O distances are in the range 1.896(9)−2.092(9) Å, and the trans and cis O−Sb−O bond angles are in the ranges 166.0 (4)−180.0 (4)° and 78.8(2)−99.0 (4)°, respectively. Hence, the SbO6 octahedron is slightly distorted from the perfect octahedron. These bond distances and angles are similar to those reported in K3BSb4O1315c and other related compounds.15 Both B(1) and B(2) are in a planar triangular geometry with B−O distances in the range 1.307(17)− 1.420(15) Å. Eu(1) is 8-coordinated whereas Eu(2) is 9B

DOI: 10.1021/acs.inorgchem.6b01790 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry Table 2. Important Bond Lengths (Å) for Four Compoundsa Compounds

SmSb2BO8

EuSb2BO8

GdSb2BO8

TbSb2BO8

Ln(1)−O(2) Ln(1)−O(3)#1 Ln(1)−O(1)#1 Ln(1)−O(10)#2 Ln(1)−O(10)#3 Ln(1)−O(11)#3 Ln(1)−O(11)#2 Ln(1)−O(9) Ln(2)−O(1)#1 Ln(2)−O(8)#5 Ln(2)−O(8)#4 Ln(2)−O(7)#2 Ln(2)−O(7)#3 Ln(2)−O(6)#6 Ln(2)−O(9) Ln(2)−O(12)#6 Ln(2)−O(4)#6 Sb(1)−O(5) Sb(1)−O(7) Sb(1)−O(7)#7 Sb(1)−O(8) Sb(1)−O(8)#7 Sb(1)−O(3) Sb(2)−O(9) Sb(2)−O(9)#3 Sb(2)−O(7) Sb(2)−O(7)#3 Sb(2)−O(10) Sb(2)−O(10)#3 Sb(3)−O(11) Sb(3)−O(11)#7 Sb(3)−O(10)#7 Sb(3)−O(10) Sb(3)−O(4)#6 Sb(3)−O(6) Sb(4)−O(12) Sb(4)−O(12)#8 Sb(4)−O(8)#9 Sb(4)−O(8)#10 Sb(4)−O(11)#8 Sb(4)−O(11) B(1)−O(2) B(1)−O(1) B(1)−O(3) B(2)−O(5) B(2)−O(4) B(2)−O(6)

2.137(2) 2.387(2) 2.514(13) 2.485(13) 2.510(2) 2.579(13) 2.579(13) 2.653(2) 2.231(2) 2.426(13) 2.426(13) 2.499(13) 2.499(13) 2.780(18) 2.717(2) 2.641(2) 2.525(17) 1.892(19) 1.950(2) 1.966(13) 1.966(13) 1.983(13) 1.983(13) 1.943(7) 1.943(7) 1.944(13) 1.944(13) 1.964(13) 1.965(13) 1.947(13) 1.947(13) 1.971(13) 1.971(13) 2.015(18) 2.082(18) 1.952(12) 1.952(12) 1.955(7) 1.955(7) 1.972(3) 1.972(3) 1.380(4) 1.291(4) 1.360(4) 1.332(3) 1.381(4) 1.410(3)

2.101(11) 2.348(9) 2.478(6) 2.478(6) 2.481(9) 2.591(6) 2.591(6) 2.640(8) 2.224(9) 2.419(6) 2.419(6) 2.483(6) 2.483(6) 2.509(9) 2.624(9) 2.708(9) 2.739(8) 1.896(9) 1.963(9) 1.967(6) 1.967(6) 1.971(6) 1.971(6) 1.955(3) 1.955(3) 1.957(6) 1.957(6) 1.964(6) 1.964(6) 1.952(6) 1.952(6) 1.971(6) 1.971(6) 2.025(8) 2.092(9) 1.937(3) 1.937(3) 1.942(6) 1.942(6) 1.958(6) 1.958(6) 1.307(17) 1.387(16) 1.387(17) 1.322(16) 1.371(15) 1.420(15)

2.106(7) 2.327(6) 2.467(7) 2.470(4) 2.470(4) 2.588(4) 2.588(4) 2.617(6) 2.234(7) 2.422(4) 2.422(4) 2.482(4) 2.482(4) 2.516(7) 2.625(6) 2.688(6) 2.725(7) 1.906(7) 1.961(6) 1.964(4) 1.965(4) 1.969(4) 1.969(4) 1.951(4) 1.951(4) 1.953(2) 1.953(2) 1.962(4) 1.962(4) 1.939(4) 1.939(4) 1.966(4) 1.966(4) 2.026(7) 2.079(6) 1.932(4) 1.932(4) 1.937(2) 1.937(2) 1.971(5) 1.971(5) 1.270(15) 1.369(15) 1.455(14) 1.304(13) 1.406(12) 1.417(12)

2.080(6) 2.311(6) 2.448(4) 2.448(4) 2.460(6) 2.591(4) 2.591(4) 2.606(5) 2.212(6) 2.413(4) 2.413(4) 2.476(4) 2.476(4) 2.501(5) 2.629(6) 2.697(6) 2.706(6) 1.910(6) 1.959(4) 1.959(4) 1.962(4) 1.962(4) 1.974(6) 1.948(2) 1.948(2) 1.958(4) 1.958(4) 1.964(4) 1.964(4) 1.941(4) 1.941(4) 1.977(4) 1.977(4) 2.031(6) 2.083(6) 1.930(2) 1.930(2) 1.933(5) 1.933(5) 1.967(4) 1.967(4) 1.294(12) 1.381(11) 1.439(11) 1.311(11) 1.391(11) 1.408(11)

octahedra. The Sb(2)-O and Sb(4)-O chains are further bridged by Sb(1)O6 octahedra via corner-sharing into a 2D [Sb3O12]9− layer with 6-MRs and 3-MRs windows. These layers feature similar hexagonal tungsten oxide (HTO)-type topologies27 such as the Mo3O126− layers in A2(MoO3)3(SeO3) (A = Rb+ and Tl+)27c (Figures 1a, and S7). Both of the Sb3O129− and Mo3O126− layers exhibit 6-MRs and 3-MRs windows. Neighboring 2D layers are further connected by 1D [SbBO7]6− chains via corner-sharing into 3D [Sb4BO14]5− anionic networks with 1D 6-MRs tunnels along the a-axis (Figure 1c). B(1)O3 groups are grafted into 1D 6-MRs tunnels of the [Sb4BO14]5− networks forming one B−O−Sb bridge per borate group, leading to the formation of an unusual 3D [Sb2BO8]3− network (Figure 1d). Eu(1)3+ ions are also located at the above 1D tunnels, and they are bridged by a B(1)O3 group into 1D [EuBO3] chains (Figure 2b) (Figure 1d). The Eu(2) atoms are situated at the centers of the 6-member rings of the [Sb3O12]9− layer; hence, a 2D [EuSb3O12]6− europium antimonite layer is formed (Figure 2d). The calculated total bond valence for Eu(1), Eu(2), Sb(1), Sb(2), Sb(3), Sb(4), B(1), and B(2) is 3.13, 3.01, 5.79, 5.73, 5.26, 5.93, 3.10, and 3.01, respectively. The results reveal that the Eu, Sb, and B atoms are in an oxidation state of +3, +5, and +3. We usually adopted the formula “s = exp[(ro − r)/B]”26 to calculate the bond valence, where s is the bond valence, ro is the standard bond length, r is the real bond length, and B is an empirically determined parameter. The error of the bond valence calculation mainly comes from the deviation between ro and r. The difference of the calculated BVS between Sb(3) and other Sb atoms (Sb(2), Sb(3), Sb(4)) is due to their different coordination environments. Sb(1)O6, Sb(2)O6, and Sb(4)O6 locate within the Sb 3 O 12 9− layers in which these SbO 6 octahedra are interconnected, while Sb(3)O6 octahedra connect with BO3 groups to form SbBO76− chains. We have carried out bond valence calculations for other related Sb-containing compounds. The bond valence of Sb in ASbV2O8 (A= K, Rb, Cs, Tl)14e and Ca2Sb2O714f is 5.59, 5.71, 5.65, 5.76, and 5.76, respectively. As previously reported, the bond valence of Sb in KSbB2O6,15a BaSb2B4O12,15a and Rb2SbB3O815e was 5.63, 5.61, and 5.70, respectively. Although the calculated bond valences of Sb are larger than the expected value, this phenomenon often appears in the compounds which contain a +5 oxidation state of Sb. Interestingly, the SbO6 octahdra in EuBSb2O8 form an independent 3D Sb2O74− anionic framework via corner-sharing with 1D tunnels of Sb3 and Sb6 MRs along the a axis (Figure S5). As both EuBSb2O8 and K3Sb4BO1315c belong to the antimony-rich phase but with different counter cations, it is interesting to compare their structures. In K3Sb4BO13, (Sb3O9)n layers are connected to two neighbors by BO3 triangles on one side and edge-sharing pairs of SbO6 octahedra on the other side to form a framework with 1D tunnels, extending approximately along the a and b axes, which filled with the K+ ions. However, neighboring SbO6 octahedra layers in EuSb2BO8 are bridged by Sb(3)O6 octahedra via a corner. This obvious difference mainly derives from the size of the counter cations: K+ has a larger size but similar coordination number with Eu3+; hence, K+ needs tunnels of larger size, and therefore, the (Sb3O9)n layer in the K compound connects its two neighbors by BO3 triangles on one side and edge-sharing pairs of SbO6 octahedra on the other side to create larger tunnels. In EuBSb2O8, neighboring SbO6 octahedra layers are bridged by Sb(3)O6 octahedra via

a

Symmetry transformations used to generate equivalent atoms: (#1) x − 1/2, y, −z + 1/2; (#2) −x + 1, y + 1/2, −z + 1; (#3) −x + 1, −y, −z + 1; (#4) −x + 1, −y + 1, −z + 1; (#5) −x + 1, y − 1/2, −z + 1; (#6) x − 1/2, y, −z + 3/2; (#7) x, −y + 1/2, z; (#8) −x + 3/2, y − 1/2, z + 1/2; (#9) x − 1/2, −y + 1/2, −z + 3/2; (#10) −x + 1,−y, −z + 2.

coordinated by oxygen atoms with Eu−O distances in the range 2.101(11)−2.739(8) Å; their coordination geometries can be described as distorted bicapped and tricapped trigonal prisms, respectively (Figure 2a, 2c). Sb(3)O6 octahedra are bridged by B(2)O3 groups into 1D [SbBO7]6− chains (Figure 1b). Sb(2)O6 octahedra are cornersharing into a 1D chain along the b axis, as are Sb(4)O6 C

DOI: 10.1021/acs.inorgchem.6b01790 Inorg. Chem. XXXX, XXX, XXX−XXX

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Figure 1. View of the [Sb3O12]9− layer along the c-axis (a), the 1D [SbBO7]6− chain along the a-axis (b), the [Sb4BO14]5− network along the a-axis (c), and the [Sb2BO8]3− network along the a-axis (d).

show a downtrend. These TGA and DSC curves show that compounds 1−4 decompose upon further increase of temperature. To verify the decomposed products of compounds 1−4, powder samples were calcined under 1100 °C for 1 day; the residuals were confirmed by PXRD to be the corresponding Ln2O3 (Ln = Sm, Eu, Gd, and Tb), Sb2O5, and some other unknown substances (Figure S1). UV and IR Spectra. The UV absorption spectral measurements revealed that compounds 2−4 exhibit little absorption in the wavelength region from 400 to 2500 nm (Figure S3). However, compound 1 shows symbolic sharp absorption peaks at 402, 1067, 1189, 1221, and 1379 nm. These absorption peaks derived from the characteristic f−f or f−d transition associated with Sm3+ ions present in the compound.21 Optical diffuse reflectance spectra show that compounds 1−4 are wide band gap semiconductors with band gaps of 3.54, 3.46, 3.48, and 3.53 eV, respectively (Figure S2). IR spectra of compounds 1−4 exhibit high transmittance in the wavenumber region from 4000 to 1600 cm−1 (2.5−6.25 μm) (Figure S4). The strong absorption peaks of IR spectra show νas(B−O) at 1481−1492 cm−1 and 1383−1388 cm−1; νs(B−O) at 1144−1156 cm−1; νs(Sb−O) at 747−774 cm−1 and 631−638 cm−1; and ν(Sb−O antistretching and Sb−O−Sb vibrations) at 467−490 cm−1. These assignments are in accordance with other metal boroantimonates and antimonates.14,15 Luminescent Properties. The solid-state luminescent properties of compounds 1 and 4 were measured at room temperature and 77 K, respectively, whereas compound 2 was measured at both room temperature and 77 K (Figure 4). Using 404 nm excitation light, four strong characteristic emission bands of compound 1 for Sm3+ ion were detected in the visible region: 568 (4G5/2 →6H5/2), 606 (4G5/2 →6H7/2), 652, and 713 nm (4G5/2 →6H9/2), respectively (Figure 4a).21

Figure 2. Coordination geometry around the Eu(1) atom (a), and a [Eu(1)BO3] chain along the a-axis (b); the coordination geometry around the Eu(2) atom (c), and a [EuSb3O12]6− layer along the c-axis (d).

corner-sharing; hence, the network exhibits tunnels with a smaller size. The Ln-O bond lengths decrease obviously from Sm to Tb because of the so-called “lanthanide contraction”. The three axial lengths also decrease from compound 1 to 4 and the cell volume contracts about 1.42% (Table 1). However, Sb−O and B−O bonds are not affected significantly by the “lanthanide contraction” (Table 2). TGA and DSC Studies. To study the thermal behaviors of compounds 1−4, TGA and DSC were measured under N2 atmosphere (Figure 3). Compounds 1−4 are stable up to 956, 977, 955, and 947 °C, respectively. From the DSC curves of compounds 1−4, they showed endothermic peaks in the heating curves at 1050, 1037, 1015, and 1002 °C, respectively. With the increase of the lanthanide atomic number, these peaks D

DOI: 10.1021/acs.inorgchem.6b01790 Inorg. Chem. XXXX, XXX, XXX−XXX

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Figure 3. TGA and DSC curves for compounds 1 (a), 2 (b), 3 (c), and 4 (d).

Figure 4. Solid-state emission spectra of compound 1 (λex = 404 nm) at room temperature (a), compound 2 (λex = 393 nm) at 77 K and room temperature (b), and compound 4 (λex = 377 nm) at 77 K (c).

The lifetime of Sm (4G5/2) for λex, em = 397, 607 nm is measured to be about 10 μs (Figure S6a). When excited at 393

nm, compound 2 displays several emission bands in the range 550−750 nm, which are originated from the 5D0 → 7F0−4 E

DOI: 10.1021/acs.inorgchem.6b01790 Inorg. Chem. XXXX, XXX, XXX−XXX

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Figure 5. Plots of χ and 1/χ vs T for compounds 1 (a), 2 (b), 3 (c), and 4 (d). The red lines represent the linear fit of data according to the Curie− Weiss Law.

transition of the Eu3+ ion:21 572, 581 nm (5D0 →7F0), 585, 592 nm (5D0 → 7F1), 608−629 nm (5D0 → 7F2), a very weak band near the 661 nm (5D0 → 7F3) transition, and 685 and 700 nm (5D0 → 7F4) (Figure 4b). The rest of the transition bands split into some sub-bands because of the crystal field effect of the Eu3+ ions. Two 5D0 → 7F0 peaks obviously indicate that there are at least two Eu3+ local sites, which is in agreement with the results from crystallographic studies. Namely, the two Eu(III) sites have distinctively different absorption cross sections. Due to the ligand field effects, 5D0 → 7F0, 3 transitions are allowed, with 5D0 → 7F1 transitions having magnetic dipole (MD) character, while the 5D0 → 7F2, 4 transitions in the range of 608−629 nm and 685−700 nm having electric dipole (ED) character are allowed due to the absence of a symmetry center in the Eu3+ site. Crystallographic data are also confirmed by these results: Eu(1) and Eu(2) are in coordination geometries of distorted bicapped and tricapped trigonal prisms, respectively, both without an inversion center. Compound 2 emits red light due to its strongest emission peak at 620 nm. The lifetime of the Eu(5D0) for λex, em = 393, 621 nm is measured to be about 0.68 ms (Figure S6b). Fewer emission peaks than expected are observed because of the instrument resolution limit and overlapping of some emission bands. At lower temperature, such as 77 K, the lower level of 5D0 is the most likely populated one; hence, the corresponding emission spectra have much better resolution (Figure 4b). The lifetime of the Eu(5D0) for λex, em = 393, 621 nm is increased to 0.97 ms

at 77 K (Figure S6c). Under excitation at 377 nm in 77 K, compound 4 displays the characteristic emission bands of the Tb3+ ion. The emission peaks can be assigned to 5D4 → 7FJ (J = 6, 5, 4, and 3) transitions for Tb3+ ion: 488 nm (5D4 → 7F6), 540 nm (5D4 → 7F5), 585 nm (5D4 → 7F4), and 623 nm (5D4 → 7F3) (Figure 4c). Due to the splitting of the crystal field, a few additional weak bands are present at the emission bands. Compound 4 emits green light due to its strongest band being at 540 nm. But the lifetime for compound 4 is too short to be measured.21,22 Hence, compounds 1, 2, and 4 have potential application as the orange, red, and green light luminescent materials. Magnetic Properties. The magnetic properties of LnBSb2O8 [Ln = Sm (1), Eu (2), Gd (3), Tb (4)] have been measured in the temperature region from 2 to 300 K at a magnetic field of 1000 Oe (Figure 5). Plots of the molar magnetic susceptibility (χ) and corresponding reciprocal susceptibility (χ−1) versus temperature (T) are shown in Figure 5. For compounds 1 and 2, their magnetic susceptibilities seriously deviated from the Curie−Weiss law in most of the temperature regions. The effective magnetic moments (μeff) of Ln3+ (Ln = Sm, Eu) ions were evaluated to be 1.55 and 3.40 μB in compounds 1 and 2 at 300 K, respectively, which are close to their theoretical values for an isolated Sm3+ (1.55−1.65 μB) or Eu3+ ion (3.40−3.51 μB). Upon cooling, the values of μeff decrease continuously and reach 0.49 and 0.46 μB at 2 K for compounds 1 and 2, F

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respectively, which indicate the existence of antiferromagnetic interactions between magnetic centers in both compounds.23 Furthermore, for compound 2, the magnetic susceptibility (χ) increases smoothly and then tends to a plateau as T is lowered. However, as T is further lowered, χ increases again at very low temperature, which can be assigned to the existence of a few parts per million of a rare-earth metal ion with a paramagnetic ground state in the compound.24a At the lowest temperature, the value of χT approaches zero (at 2K, χT = 0.027), which indicates the J = 0 ground state of Eu3+ ions (7F0).24b For compounds 3 and 4, they obey the Curie−Weiss law at temperatures ranging from 50 to 300 K. At 300 K, the effective magnetic moments (μeff) of Ln3+ (Ln = Gd, Tb) ions were evaluated as 7.94 and 9.86 μB for compounds 3 and 4, respectively, which are similar to the standard values for the isolated Gd3+ (7.94 μB) or Tb3+ ions (9.7 μB). Upon cooling, the values of μeff decrease slightly for compounds 3 and 4, which indicates that both compounds are essentially paramagnetic.22,24 Curie constants (C) of 7.87 and 12.39 emu mol−1 K and Weiss temperatures (θ) of 0.171 and −7.8 K were given after fitting of the magnetic data in the temperature region from 50 to 300 K, respectively, for compounds 3 and 4, which indicates that there exists very weak ferromagnetic coupling interactions between neighboring Ln ions in compound 3 and antiferromagnetic coupling interactions between neighboring Ln ions in compound 4.24,25 The distances between the nearest Ln3+...Ln3+ ions are 4.2208, 4.2112, 4.1879, and 4.1559 Å, respectively, for compounds 1, 2, 3, and 4; hence, it is suggested that the magnetic exchange interactions in these compounds must be rather weak. The different magnetic behaviors of these compounds exist due to the different LnIII ions electronic configurations. More detailed information about these magnetic interactions was not performed due to the lack of suitable models available and their complicated structures.

AUTHOR INFORMATION

Corresponding Author

*Fax: (+86)591-63173121; E-mail: [email protected]. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS Our work was supported by the National Natural Science Foundation of China (Grants 21231006, 21373222, and 21401194).

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REFERENCES

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CONCLUSIONS In summary, the first series of lanthanide boroantimonates, namely, LnBSb2O8 [Ln = Sm (1), Eu (2), Gd (3), Tb (4)], have been successfully obtained through the conventional high temperature solid-state reactions. They are isostructural and exhibit novel three-dimensional (3D) frameworks composed of 2D [Sb3O12]9− layers interconnected by 1D [SbBO7]6− chains with remaining BO3 groups hanging on the walls of the 1D 6membered-ring (MR) tunnels along the a-axis. Luminescent studies show that compounds 1, 2, and 4 have potential application as the orange, red, and green light luminescent materials, respectively. It can be expected that more new lanthanide boroantimonates with novel structures as well as excellent physical properties can be synthesized through a similar procedure by changing the Sb/B ratios and reaction temperatures, and such works are underway.

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Article

ASSOCIATED CONTENT

* Supporting Information S

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.6b01790. Simulated and experimental XRD patterns, IR spectra, UV spectra, optical diffuse reflectance spectra, and decay curves for compounds 1−4 (PDF) X−ray crystallographic files in CIF format (CIF) G

DOI: 10.1021/acs.inorgchem.6b01790 Inorg. Chem. XXXX, XXX, XXX−XXX

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DOI: 10.1021/acs.inorgchem.6b01790 Inorg. Chem. XXXX, XXX, XXX−XXX