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

Abstract

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.

Cs2VOF4(IO2F2): Rationally designing a noncentrosymmetric early-transition-metal fluoroiodate

“…63,64 Firstly, for F-containing iodates, their A-site cations are alkali or alkaline-earth cations, which have a low Lewis acid strength (Table S4, ESI†). Therefore, according to the bond valence matching principle, 65,66 the terminal atoms of the counter-anions should also have relatively low residual negative charges, i.e. possessing relatively low Lewis base strengths.…”

K2MgMoP2O10 and K3Mg2MoP3O14: two new molybdophosphates exhibiting different optical anisotropies induced by variable dimensionality of the anion framework

“…In the structure of molybdophosphates, [MoO 6 ] and [PO 4 ] units are often connected to produce different structures, such as zero-dimensional (0D) Mo–O–P clusters, 32,33 1D Mo–O–P chains, 34 and 2D Mo–O–P layers. 34–40 Successful examples with new structures and special performances have been reported, such as KCsMoP 2 O 9 , 41 Cs 4 Mo 5 P 2 O 22 , 42 Cs 3 Mo 12 PO 40 , 43 Sr(MoPO 6 ) 2 , 43 Rb 2 Bi(MoO 4 )(PO 4 ), 44 Cs 6 Mo 2 P 4 O 19 , 45 and so on. Therefore, it is of great significance to study the structural evolution and properties of Mo–P–O systems.…”