Zn2(VO4)(IO3): a novel polar zinc(II) vanadium(V) iodate with a large SHG response.

The synthesis, crystal and electronic structures, and optical properties of the first zinc(II) vanadium(V) iodate, namely, Zn2(VO4)(IO3), are reported. Zn2(VO4)(IO3) crystallizes in the noncentrosymmetric (NCS) and polar space group Pc (No. 7) with a = 5.2714(8) Å, b = 10.0402(11) Å, c = 5.5070(8) Å, β = 101.326(10)°, and Z = 2. It displays a novel three-dimensional (3D) network structure composed of ZnO5, ZnO6, VO4, and IO3 polyhedra. One-dimensional (1D) chains of edge-sharing ZnO5 polyhedra and 1D chains of corner-sharing ZnO6 octahedra along the c-axis are interconnected via corner-sharing into a two-dimensional (2D) zinc oxide layer, and such layers are bridged by both VO4 tetrahedra and IO3 groups into a 3D network. The polarity in the structure is imparted by the alignment of the stereochemically active lone pairs of the iodate anions along the c-axis. The second harmonics generation (SHG) measurements on powder samples of Zn2(VO4)(IO3) under 1064-nm laser radiation revealed a large response of ∼6 × KDP, which is Type I phase-matchable. Thermal stability and optical properties, as well as theoretical calculations based on DFT methods, were also performed.