New Vanadium Selenites:\nCentrosymmetric Ca<sub>2</sub>(VO<sub>2</sub>)<sub>2</sub>(SeO<sub>3</sub>)<sub>3</sub>(H<sub>2</sub>O)<sub>2</sub>, Sr<sub>2</sub>(VO<sub>2</sub>)<sub>2</sub>(SeO<sub>3</sub>)<sub>3</sub>, and Ba(V<sub>2</sub>O<sub>5</sub>)(SeO<sub>3</sub>), and Noncentrosymmetric and Polar\nA<sub>4</sub>(VO<sub>2</sub>)<sub>2</sub>(SeO<sub>3</sub>)<sub>4</sub>(Se<sub>2</sub>O<sub>5</sub>) (A = Sr<sup>2+</sup> or Pb<sup>2+</sup>)
Jeongho Yeon (1406326)Sang-Hwan Kim (527119)Sau Doan Nguyen (1985821)Hana Lee (445860)P. Shiv Halasyamani (1261704)
Abstract
Five new vanadium selenites, Ca<sub>2</sub>(VO<sub>2</sub>)<sub>2</sub>(SeO<sub>3</sub>)<sub>3</sub>(H<sub>2</sub>O)<sub>2</sub>,\nSr<sub>2</sub>(VO<sub>2</sub>)<sub>2</sub>(SeO<sub>3</sub>)<sub>3</sub>, Ba(V<sub>2</sub>O<sub>5</sub>)(SeO<sub>3</sub>), Sr<sub>4</sub>(VO<sub>2</sub>)<sub>2</sub>(SeO<sub>3</sub>)<sub>4</sub>(Se<sub>2</sub>O<sub>5</sub>), and Pb<sub>4</sub>(VO<sub>2</sub>)<sub>2</sub>(SeO<sub>3</sub>)<sub>4</sub>(Se<sub>2</sub>O<sub>5</sub>), have\nbeen synthesized and characterized. Their crystal structures were\ndetermined by single crystal X-ray diffraction. The compounds exhibit\none- or two-dimensional structures consisting of corner- and edge-shared\nVO<sub>4</sub>, VO<sub>5</sub>, VO<sub>6</sub>, and SeO<sub>3</sub> polyhedra. Of the reported materials, A<sub>4</sub>(VO<sub>2</sub>)<sub>2</sub>(SeO<sub>3</sub>)<sub>4</sub>(Se<sub>2</sub>O<sub>5</sub>) (A = Sr<sup>2+</sup> or Pb<sup>2+</sup>) are noncentrosymmetric\n(NCS) and polar. Powder second-harmonic generation (SHG) measurements\nrevealed SHG efficiencies of approximately 130 and 150 × α–SiO<sub>2</sub> for Sr<sub>4</sub>(VO<sub>2</sub>)<sub>2</sub>(SeO<sub>3</sub>)<sub>4</sub>(Se<sub>2</sub>O<sub>5</sub>) and Pb<sub>4</sub>(VO<sub>2</sub>)<sub>2</sub>(SeO<sub>3</sub>)<sub>4</sub>(Se<sub>2</sub>O<sub>5</sub>), respectively. Piezoelectric charge constants of 43 and\n53 pm/V, and pyroelectric coefficients of −27 and −42\nμC/m<sup>2</sup>·K at 70 °C were obtained for Sr<sub>4</sub>(VO<sub>2</sub>)<sub>2</sub>(SeO<sub>3</sub>)<sub>4</sub>(Se<sub>2</sub>O<sub>5</sub>) and Pb<sub>4</sub>(VO<sub>2</sub>)<sub>2</sub>(SeO<sub>3</sub>)<sub>4</sub>(Se<sub>2</sub>O<sub>5</sub>), respectively.\nFrequency dependent polarization measurements confirmed that the materials\nare not ferroelectric, that is, the observed polarization cannot be\nreversed. In addition, the lone-pair on the Se<sup>4+</sup> cation\nmay be considered as stereo-active consistent with calculations. For\nall of the reported materials, infrared, UV–vis, thermogravimetric,\nand differential thermal analysis measurements were performed. Crystal\ndata: Ca<sub>2</sub>(VO<sub>2</sub>)<sub>2</sub>(SeO<sub>3</sub>)<sub>3</sub>(H<sub>2</sub>O)<sub>2</sub>, orthorhombic, space group <i>Pnma</i> (No. 62), <i>a</i> = 7.827(4) Å, <i>b</i> = 16.764(5) Å, <i>c</i> = 9.679(5) Å, <i>V</i> = 1270.1(9) Å<sup>3</sup>, and <i>Z</i> = 4; Sr<sub>2</sub>(VO<sub>2</sub>)<sub>2</sub>(SeO<sub>3</sub>)<sub>3</sub>, monoclinic, space group <i>P</i>2<sub>1</sub><i>/c</i> (No. 12), <i>a</i> = 14.739(13) Å, <i>b</i> = 9.788(8) Å, <i>c</i> = 8.440(7) Å,\nβ = 96.881(11)°, <i>V</i> = 1208.8(18) Å<sup>3</sup>, and <i>Z</i> = 4; Ba(V<sub>2</sub>O<sub>5</sub>)(SeO<sub>3</sub>), orthorhombic, space group <i>Pnma</i> (No. 62), <i>a</i> = 13.9287(7) Å, <i>b</i> = 5.3787(3) Å, <i>c</i> = 8.9853(5) Å, <i>V</i> = 673.16(6) Å<sup>3</sup>, and <i>Z</i> = 4; Sr<sub>4</sub>(VO<sub>2</sub>)<sub>2</sub>(SeO<sub>3</sub>)<sub>4</sub>(Se<sub>2</sub>O<sub>5</sub>), orthorhombic, space group <i>Fdd</i>2 (No. 43), <i>a</i> = 25.161(3) Å, <i>b</i> = 12.1579(15) Å, <i>c</i> = 12.8592(16)\nÅ, <i>V</i> = 3933.7(8) Å<sup>3</sup>, and <i>Z</i> = 8; Pb<sub>4</sub>(VO<sub>2</sub>)<sub>2</sub>(SeO<sub>3</sub>)<sub>4</sub>(Se<sub>2</sub>O<sub>5</sub>), orthorhombic,\nspace group <i>Fdd</i>2 (No. 43), <i>a</i> = 25.029(2)\nÅ, <i>b</i> = 12.2147(10) Å, <i>c</i> = 13.0154(10) Å, <i>V</i> = 3979.1(6) Å<sup>3</sup>, and <i>Z</i> = 8.
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