Deep-ultraviolet transparent alkali metal–rare earth metal sulfate NaY(SO₄)₂·H₂O as a nonlinear optical crystal: synthesis and characterization

Abstract

A new alkali metal-rare earth metal sulfate with the formula NaY(SO4)2.H2O has been synthesized using a mild hydrothermal method. It crystallizes in the noncentrosymmetric trigonal space group P3121 (No. 152)...

Synthesis, Crystal Structure, and Nonlinear Optical Property of an Anhydrous Sulfate KTb(SO4)2

“…A Tb atom is connected to eight O atoms to form a [TbO 8 ] polyhedron, where the Tb–O bond lengths are in the range of 2.2767–2.5562 Å (Figure b), which is consistent with the results reported in the previous literature, indicating their rationality. An S atom is linked to four O atoms to form a [SO 4 ] tetrahedra with the S–O bond lengths of 1.426(6)–1.496(6) Å and the O–S–O bond angles of 109.3(4)–114.0(4)° (Figure c), which is also reasonable and confirmed by previous papers. ,, It can be noted that the O in [TbO 8 ] comes from 7 [SO 4 ], and 2 of them come from the same [SO 4 ] (Figure a). With S as the center, the bonding situation among K, Tb, S, and O atoms can be clearly observed; one [SO 4 ] group is neighbored to four Tb atoms and two K atoms through O atom (Figure b).…”

“…Crystal structure analysis showed that it crystallized in the orthorhombic space group P2 1 2 1 2 1 with cell parameters a = 5.43950 (10) 1c), which is also reasonable and confirmed by previous papers. 37,38,51 It can be noted that the O in [TbO 8 ] comes from 7 [SO 4 ], and 2 of them come from the same [SO 4 ] (Figure 2a). With S as the center, the bonding situation among K, Tb, S, and O atoms can be clearly observed; one [SO 4 ] group is neighbored to four Tb atoms and two K atoms through O atom (Figure 2b).…”

“…The test result of KTSO powder infrared absorption spectrum is shown in Figure S7; only a few absorption peaks are located at around 1125 and 609 cm −1 respectively, which are all attributed to the stretching vibration (1125 cm −1 ) and bending vibration (609 cm −1 ) of the [SO 4 ] group, and these attributions are consistent with the results reported in previous literature. 37,38 The UV−vis-NIR transmission spectra of KTSO were tested using bulk crystals, and the results are shown in Figure S8(a). The result of the powder UV−vis reflectance spectroscopy test of KTSO is shown in Figure S8(b); the experimental results show that the absorption cutoff edge is about 407 nm, which corresponds to a computed optical bandwidth of 3.04 eV.…”

“…As another non-π-conjugated material, the study of sulfate as an NLO material has been long neglected. Until recent years, sulfates as a potential UV/Deep UV NLO materials have gradually drawn people’s attention, and thus some sulfate NLO materials have emerged successively, for instance, Li 8 NaRb 3 (SO 4 ) 6 ·2H 2 O, NH 4 NaLi 2 (SO 4 ) 2 , NaBi­(SO 4 ) 2 ·H 2 O, NaCe­(SO 4 ) 2 ·H 2 O, NaY­(SO 4 ) 2· H 2 O, Rb 3 In­(SO 4 ) 3 , K 2 Mn 3 (SO 4 ) 3 F 2 ·4H 2 O, Te 2 O 3 (SO 4 ), KBiCl 2 SO 4 , K 3 Bi 2 Cl 5 O 2 (SO 4 ) 2 , etc. Nevertheless, the examples of sulfate systems as NLO materials are still extremely rare.…”

Structural Features of Y2O2SO4 via DFT Calculations of Electronic and Vibrational Properties

“…Traditionally, the search of nonlinear optical (NLO) materials focused on borate systems [22], on the other hand, several NLO sulfate crystals were synthesized in recent years [23][24][25][26][27]. As to the Re 2 O 2 SO 4 oxysulfates, the crystal structure of Nd 2 O 2 SO 4 [28] was solved in the non-centrosymmetric (I222) space group and thus this class of compounds can be a candidate for NLO materials.…”