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

By introducing the d0 metal cation Mo6+ into phosphates, two new molybdophosphates, K2MgMoP2O10 and K3Mg2MoP3O14, were synthesized by spontaneous crystallization, and their structures were determined by single-crystal X-ray diffraction. K2MgMoP2O10 shows a two-dimensional layer composed of the uncommon eight-membered ring [Mo2P2O16] formed by [MoO6] and [PO4], while K3Mg2MoP3O14 shows isolated [MoP3O14] clusters composed of [MoO5] and [PO4]. K2MgMoP2O10 and K3Mg2MoP3O14 have UV cut-off wavelengths of 277 and 271 nm, respectively, which are significantly shorter than those of most recently published molybdophosphates. To the best of our acknowledge, K2MgMoP2O10 exhibits the largest birefringence (a calculated value of 0.187 at 546 nm) among reported alkali metal or alkaline earth metal molybdophosphates, which provides a way to explore new birefringent materials. First-principles analysis of the electronic structure shows that the large birefringence of K2MgMoP2O10 mainly originates from the [MoO6] units.