New Quaternary Tellurite and Selenite: Synthesis, Structure, and Characterization of Centrosymmetric InVTe₂O₈ and Noncentrosymmetric InVSe₂O₈

Abstract

Two new quaternary mixed metal oxide materials--InVTe(2)O(8) and InVSe(2)O(8)--have been synthesized, as crystals and pure bulk powders by standard solid-state reactions using In(2)O(3), V(2)O(5), and TeO(2) (or SeO(2)) as reagents. The crystal structures of the reported materials were determined using single-crystal X-ray diffraction. InVTe(2)O(8) crystallizes in the monoclinic centrosymmetric space group P2(1)/n (No. 14), with unit-cell parameters of a = 7.8967(16) Å, b = 5.1388(10) Å, c = 16.711(3) Å, β = 94.22(3)°, and Z = 4, and InVSe(2)O(8) crystallizes in the noncentrosymmetric space group Pm (No. 6) with unit-cell parameters of a = 4.6348(9) Å, b = 6.9111(14) Å, c = 10.507(2) Å, β = 97.77(3)°, and Z = 2. While the centrosymmetric InVTe(2)O(8) shows a two-dimensional (2D) layered structure composed of InO(6) octahedra, VO(4) tetrahedra, and TeO(4) polyhedra, the noncentrosymmetric InVSe(2)O(8) exhibits a three-dimensional (3D) framework structure with distorted InO(6) octahedra, VO(5) square pyramids, and SeO(3) polyhedra. Powder second-harmonic generation (SHG) measurements on InVSe(2)O(8), using 1064-nm radiation, indicate that the material has a SHG efficiency ~30 times that of α-SiO(2). Additional SHG measurements reveal that the material is not phase-matchable (Type 1). Infrared, ultraviolet-visible light (UV-vis) diffuse reflectance, and thermogravimetric analyses for the two compounds are also presented, as are dipole moment calculations.

Metal–organic frameworks as competitive materials for non-linear optics

“…Accordingly, elongation of bonds along the z-axis occurs, resulting in a lower symmetry. [101][102][103][104][105][106][107][108][109] Unfortunately, such an approach cannot warrant the expected result; therefore, the main task is controlling the macroscopic symmetry of the system. 110 In the crystallization of a material, its symmetry may be affected not only by the selected cation, but also by its environment arising from the interaction of hydrogen bonds.…”

A new one-dimensional strontium vanadium tellurite, Sr7V4Te12O41

“…Vanadium tellurites have been investigated extensively due to their rich structural chemistry and interesting physical properties, such as second harmonic generation (SHG) (Xiao et al, 2003;Hou et al, 2005;Jung et al, 2006;Zhang et al, 2010;Glor et al, 2011;Lee et al, 2011;Bae et al, 2016). Tellurites, i.e.…”

“…Te 4+ O x , are often observed in various unusual structures attributable to the presence of stereo-active lone-pair electrons, which serve as structure-directing agents (Guesdon & Raveau, 2000;Halasyamani, 2004). In addition, the asym-metric coordination environment of Te 4+ O x (x = 3, 4, or 5) polyhedra may form various structural motifs, including isolated clusters, chains, layers, and three-dimensional networks (Guesdon & Raveau, 2000;Xiao et al, 2003;Hou et al, 2005;Jung et al, 2006;Kim & Halasyamani, 2008;Zhang et al, 2010;Glor et al, 2011;Lee et al, 2011;Bae et al, 2016). Similarly, vanadates, i.e.…”

“…Similarly, vanadates, i.e. V 5+ O x , show rich structural features because of their various coordination geometries, such as VO 4 tetrahedra, VO 5 square pyramids or trigonal bipyramids, and VO 6 octahedra (Xiao et al, 2003;Hou et al, 2005;Jung et al, 2006;Zhang et al, 2010;Glor et al, 2011;Lee et al, 2011;Bae et al, 2016). With respect to known alkaline-earth vanadium tellurites, only two strontium vanadium tellurites, namely Sr(V 2 O 5 )(TeO 3 ) (space group P1, No.…”

Effect of polarizable lone pair cations on the second-harmonic generation (SHG) properties of noncentrosymmetric (NCS) Bi2−xYxTeO5(x = 0–0.2)

“…3,4 Due to the flexible framework architectures they form with their lone pairs, tellurites can further exhibit a much richer structural chemistry when combined with many transition metal cations. 1 Among these, tellurites, i.e., oxide materials containing Te 4+ , are of great significance.…”