(N₂H₆)[HPO₃F]₂: maximizing the optical anisotropy of deep-ultraviolet fluorophosphates

Although phosphates are a rich source of deep-ultraviolet optical materials, the realization of large optical anisotropy in them still remains a challenge because of the small polarizability anisotropy of [PO₄] units. Inspired by the fluoridation strategy and hydrogen bond interaction, a new metal-free monofluorophosphate, (N₂H₆)[HPO₃F]₂, was synthesized, which exhibits a large birefringence (cal. 0.077) and wide band gap (∼6.51 eV). Such a large birefringence in (N₂H₆)[HPO₃F]₂ sets a new record among available fluorophosphates, and the [HPO₃F] unit is theoretically confirmed to be a new birefringence-active unit.