Tailored Synthesis of a Nonlinear Optical Phosphate with a Short Absorption Edge

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.