Effect of Mo/P Ratios on Dimensions: Syntheses, Structures, and Properties of Three New Molybdophosphates.

Mo(VI)-containing phosphates are widely used in catalyses, ion batteries, and nonlinear optical (NLO) crystals. However, few strategies can effectively guide the syntheses of the Mo(VI)-containing phosphates. In this paper, three new Mo(VI)-containing phosphates, Cs3Mo12PO40, LiK(MoPO6)2, and Sr(MoPO6)2, with different dimensions have been successfully synthesized by adjusting the Mo/P ratios. Interestingly, Cs3Mo12PO40 is a classic Keggin-type polyoxometalate composed of zero-dimensional (0D) [Mo12PO40]3- clusters, whereas LiK(MoPO6)2 and Sr(MoPO6)2 have three-dimensional (3D) [MoO2O4P]∞ frameworks consisting of MoO6 octahedra and PO4 tetrahedra in a 1/1 ratio. Detailed structural comparisons of Mo(VI)-containig phosphates indicate that the Mo/P ratios have a significant effect on the structural dimensions. Further, the optical properties and thermal stabilities of Cs3Mo12PO40, LiK(MoPO6)2, and Sr(MoPO6)2 are also determined.