Two Indium Sulfate Tellurites: Centrosymmetric In₂(SO₄)(TeO₃)(OH)₂(H₂O) and Non-centrosymmetric In₃(SO₄)(TeO₃)₂F₃(H₂O)

Abstract

Two new indium sulfate tellurites, namely, In 2 (SO 4 )(TeO 3 )-(OH) 2 (H 2 O) and In 3 (SO 4 )(TeO 3 ) 2 F 3 (H 2 O), were synthesized by hydrothermal method in a one-pot reaction. Their pure phase yields have been successfully optimized to 76% and 21%, respectively. In 2 (SO 4 )(TeO 3 )-(OH) 2 (H 2 O) crystallized in centrosymmetric (CS) space group P2 1 /n, while In 3 (SO 4 )(TeO 3 ) 2 F 3 (H 2 O) formed a non-centrosymmetric (NCS) and chiral space group P2 1 2 1 2 1 . The CS compound features a 2D layered structure composed of 2D indium oxide layers decorated by sulfate tetrahedra and tellurite groups. The NCS compound displays a 3D network consisting of indium tellurite layers bridged by sulfate tetrahedra. Powder second harmonic generation measurements disclosed that In 3 (SO 4 )(TeO 3 ) 2 F 3 (H 2 O) exhibits a weak frequency-doubling efficiency about 11% of the commercial KDP. Its powder laser damage threshold quantity was estimated to be 79.6 MW/cm 2 , which is about 36 times that of AGS. The two samples present wide optical band gaps of 4.86 and 4.10 eV, respectively, which were determined by Te, In, and O atoms based on density functional theory calculations.

Sb4O3(TeO3)2(HSO4)(OH): An Antimony Tellurite Sulfate Exhibiting Large Optical Anisotropy Activated by Lone Pair Stereoactivity

“…The absorption peaks at about 682, 600, and 457 cm –1 are ascribed to the bending vibrations of S–O bonds and the stretching vibrations of Te–O and Sb–O bonds. These assignments are consistent with the structural analysis. − …”

“…S(1) is four-coordinated with the bond lengths filling in the range of 1.452(2)–1.459(2) Å. All of the bond lengths are reasonable according to the compounds observed previously. − The calculated bond valence sum (BVS) for S(1), Te(1), Sb(1), and Sb(2) atoms are 6.26, 3.80, 3.47, and 3.00, respectively. The small BVS value of Te(1) (3.80) and the large value of Sb(1) (3.47) may be caused by their lone pair effect.…”

“…The value is larger than those of many Sb-based birefringent crystals. 57−61 More importantly, the value exceeds those of the most reported metal sulfate tellurites, In 2 (TeO 3 )(SO 4 )(OH) 2 (H 2 O) (0.0561 @ 1064 nm), 45 Ga 2 (TeO 3 )(SO 4 )(OH) 2 (0.1029 @ 1064 nm), 44 Y 3 (TeO 3 ) 2 (SO 4 ) 2 (OH)(H 2 O) (0.092 @ 532 nm), 25 and Zn 4 (Te 3 O 7 ) 2 (SO 4 ) 2 (H 2 O) (0.084 @ 1064 nm) 44 is lower than that of Hg 3 (Te 3 O 8 )(SO 4 ) (0.184 @ 532/0.166 @ 1064 nm), 44 in which, in addition to the contribution of the SCALP effect of the Te 4+ cation, the large deformability of Hg 2+ also further promotes the birefringence. Therefore, it is speculated that the introduction of the "extra" SCALP cation Sb 3+ may further enhance the birefringence of sulfate tellurites, and the optical property of Sb 4 O 3 (TeO 3 ) 2 (HSO 4 )(OH) may be determined by the synergistic effect of the SCALP effect of both Sb 3+ and Te 4+ cations.…”

Anhydrous copper tellurite disulfate Cu3TeO3(SO4)2 featuring the coexistence of spin singlets and a long-range antiferromagnetic order

“…There are several anhydrous tellurite sulfates of post-transition metals, lanthanides and actinides. 3–6 All of them, however, exhibit either diamagnetic or paramagnetic responses. Besides, there are few hydrous and/or hydroxy tellurite sulfates of transition and rare-earth metals with versatile crystal structures and magnetic behaviour.…”

Cd3(PO4)(TePO6): A Novel Cadmium Tellurite‐Phosphate featuring a {[TePO6]3−}∞ Chain

“…It is well known that both tellurite and phosphates are main sources for NLO materials in the ultraviolet region. [23][24][25][26][27][28][29][30] Therefore, it has a high possibility for telluritephosphates showing promising NLO performances. Unfortu-nately, most of these compounds crystallize with centrosymmetric structures, excluding their potentials as new NLO materials.…”