화학공학소재연구정보센터
Inorganic Chemistry, Vol.52, No.3, 1488-1495, 2013
New Molybdenum(VI) Phosphates: Synthesis, Characterization, and Calculations of Centrosymmetric RbMoO2PO4 and Noncentrosymmetric Rb4Mo5P2O22
Two new molybdenum(VI) phosphates, RbMoO2PO4 and Rb4Mo5P2O22, have been synthesized by standard solid-state reactions, and their structures were determined by single-crystal X-ray diffraction. The former is centrosyrnmetric, whereas the latter is noncentrosymmetric and chiral. Their crystal structures both consist of corner- and edge-shared MoO6 octahedra, PO, tetrahedra, and RbOn (n = 8 or 10) polyhedra and exhibit three- and one-dimensional structures, respectively. Powder second-harmonic generation (SHG) measurements revealed an SHG efficiency of approximately 1.4 X KH2PO4 (KDP) for Rb4Mo5P2O22. Thermal analysis, infrared and UV-vis-NIR diffuse reflectance spectroscopy, and electronic band structure calculations were also performed on the reported materials. Crystal data are the following: RbMoO2PO4, orthorhombic, space group Fddd (No. 70), a = 11.012(5) angstrom, b = 12.403(5) angstrom, c = 15.839(7) angstrom, V = 2163.3(16) angstrom(3), and Z = 16; Rb4Mo5P2O22, orthorhombic, space group C222(1) (No. 20), a = 6.5300(5) angstrom, b = 19.7834(18) angstrom, c = 17.3451(15) angstrom, V = 2240.7(3) angstrom(3), and Z = 4.