Studies on Three 3D Bimetallic Tellurates: Including a Second-Order NLO Material with <i>d</i>¹⁰-Zn²⁺ and SOJT-Effect Te⁴⁺/Mo⁶⁺ Cations

Three 3D bimetallic tellurates, Zn₃Te^IV₂MoO₁₀ (<b>1</b>), Zn₃Te^IVMo₂O₁₁ (<b>2</b>), and CdNi₂Te^VIO₆ (<b>3</b>), have been obtained through high-temperature solid-phase reactions. <b>1</b> exhibits a 3D architecture containing <i>d</i>¹⁰-Zn²⁺/SOJT-effect Te⁴⁺/Mo⁶⁺ cations and irregular 1D 6-/12-MR channels which are constructed by ZnO₆/ZnO₅/TeO₃/MoO₄ groups via the edge-/vertex-sharing modes. Both <b>2</b> and <b>3</b> also display 3D framework structures, which are, respectively, formed by the interconnection of ZnO₆/TeO₃/MoO₆ and CdO₈/NiO₆/TeO₆ units. The TG/DTG and UV-vis diffuse reflectance spectra for <b>1</b>, <b>2</b>, and <b>3</b>, energy levels for <b>1</b> and <b>2</b>, magnetic property for <b>3</b>, and SHG response for <b>1</b> were systematically studied. The experimental results revealed that <b>1</b> possessed a good SHG response (∼0.9 × KDP, 105-150 μm), displayed a wide transmission range (369-800 nm), and high thermal stability (25-883 °C). Moreover, the dipole moments for ZnO₆ (Zn1O₆: 1.61 D, Zn2O₆: 1.33 D)/ZnO₅ (2.32 D)/TeO₃ (Te1O₃: 11.12 D/Te2O₃: 11.31 D)/MoO₄ (1.51 D) units and the band gap/partial DOS/total DOS for <b>1</b> were calculated and established. These results indicated that <b>1</b> could act as a new second-order NLO material in the visible region.