Synthesis, Crystal Structure, and Properties of Bi₃TeBO₉ or Bi₃(TeO₆)(BO₃): A Non‐Centrosymmetric Borate–Tellurate(VI) of Bismuth

Abstract

Pale-yellow single crystals of the new borate tellurate(VI) Bi TeBO were obtained by reaction of stoichiometric amounts of Bi O , B O , and Te(OH) at 780 °C. The non-centrosymmetric crystal structure (P6 , Z=2, a=8.7454(16), c=5.8911(11) Å, 738 refl., 43 param, R1=0.037, wR2=0.093) contains isolated trigonal-planar BO units and nearly undistorted TeO octahedra. The Bi cations are located in between in octahedral voids. The BiO octahedra are significantly distorted to a [3+3] pattern (2.25/2.50 Å) due to the ns configuration. According to the structural features, the formula can be written as Bi (TeO )(BO ). Alternatively, the structure can also be described as hcp of oxygen with Te and Bi in octahedral voids and B in trigonal- planar voids. The vibrational spectra show the typical features of BO and TeO units with a significant B/ B isotopic splitting of the IR-active B-O valence mode (1248 and 1282 cm ). The UV/Vis spectrum shows an optical band edge with an onset around 480 nm (2.6 eV). MAS-NMR spectra of B show an anisotropic signal with a quadrupole coupling constant of C =2.55 MHz. and a very small deviation from rotational symmetry (η=0.2). The isotropic chemical shift is 20.1 ppm. The second harmonic generation (SHG) test was positive with an activity comparable to potassium dihydrogen phosphate (KDP). Bi TeBO decomposes in air at 825 °C to Bi TeO .

Sb6O7(SO4)2: A Promising Ultraviolet Nonlinear Optical Material with an Enhanced Second‐Harmonic‐Generation Response Activated by SbIII Lone‐Pair Stereoactivity

“…A comparison of the signals reveals that the title compound displayed a SHG efficiency of about 2.0×KDP over the same particle range of 150–212 μm (Figure 2 d), and it is type I phase‐matchable, according to the rule proposed by Kurtz and Perry [51] . The value is comparable to those of sulfates, such as NH 4 NaLi 2 (SO 4 ) 2 (1.1×KDP), (NH 4 ) 2 Na 3 Li 9 (SO 4 ) 7 (0.5×KDP), [36] and Li 8 NaRb 3 (SO 4 ) 6 ⋅ 2 H 2 O (0.5×KDP), [35] as well as antimony sulfates, such as CsSbF 2 SO 4 (3.0×KDP), [42] (NH 4 )SbCl 2 (SO 4 ) (1.7×KDP), [56] RbSbSO 4 Cl 2 (2.7×KDP), [45] and Rb 2 SO 4 ⋅ SbF 3 (0.3×KDP), [47] Therefore, compound 1 is promising as a good UV NLO material, owing to the high stability, large SHG response, and phase matchability.…”

“…It is well known that the SHG responses or birefringence can be enhanced by introducing an additional distortive structural unit, that is, cations with a stereochemically active lone pair (SCALP). Typical examples include Bi 3 TeO 6 OH(NO 3 ) 2 , [33] Bi(IO 3 )F 2 , [34] Bi 3 (TeO 6 )(BO 3 ), [35] Pb 2 BO 3 I, [36] Pb 2 (NO 3 ) 2 (H 2 O)F 2 , [19] and Pb 2 B 5 O 9 I [37] . In comparison, it is noteworthy that antimony(III)‐based UV NLO materials are very limited [38–43] .…”

Bi3TeBO9: electronic structure, optical properties and photoinduced phenomena

“…Powder synthesis and XRD phase analysis BTBO powders were synthesized by means of conventional solid-state reaction route, similarly to the procedure described by Daub et al [6]. The molar ratio of used precursor compounds: Bi 2 O 3 (SIAL, 99.95%), TeO 2 (MERCK, 99.99%) and B 2 O 3 (SIAL, 99.999%), was 3:2:1.1, respectively.…”

“…Recently, Bi 3 TeBO 9 (BTBO) crystal, having very large second-order nonlinear optical susceptibilities, was discovered [6,7]. The preliminary data indicate that its nonlinear optical coefficients are, respectively, higher than in the case of the exceptional a-BiB 3 O 6 (a-BIBO) compound [7].…”

An Unprecedented Antimony(III) Borate with Strong Linear and Nonlinear Optical Responses

“…It has been widely accepted that metal cations, especially those with a stereochemical active lone pair (SCALP), can greatly enhance the birefringence and/or the SHG response of a borate . Emerging examples include borate SHG materials such as Pb 2 BO 3 X (X=Cl, Br, I), Bi 3 TeBO 9 , Pb 2 B 5 O 9 X (X=Cl, Br, I), MB 2 O 3 F 2 (M=Sn, Pb), as well as borate birefringent materials such as Sn 2 B 5 O 9 Cl . In comparison, antimony(III) borate remains a huge blank, and, thus, there is still a lack of experimental evidence on its linear and NLO properties.…”