a) Crystal structure of Ba5P6O20. Spatial packing of [P3O10]5− trimers in b) Asheets, c) B′ sheets, and d) C sheets. The B and B′ sheets are related to each other through an a glide plane. The size of the P-P-P angles is indicated. Ba atoms are omitted for clarity in (b–d). A nonlinear optical phosphate Ba5P6O20 was rationally developed by a tailored synthetic approach based on the use of flexible [P3O10]5− units. The phosphate exhibits a very short absorption edge of λ=167 nm, which is among the shortest known in phase-matchable phosphates. First-principles electronic structure analysis elucidated the origin of the changes in the optical properties, and specifically in the absorption edge, of the material. Such a tailored synthetic approach provides a new opportunity to design nonlinear optical materials with short absorption edges. Angewandte Chemie, 2015 |
