C₂H₁₂N₆C₄O₄·2H₂O and Na₂C₄O₄·3H₂O: Two Ultraviolet BirefringentCompounds with the [C₄O₄]^2– Group

Abstract

In modern optics, birefringent materials that can manipulate light polarization play important roles in lasers and information fields. The search for ultraviolet (UV) crystals with large birefringence is the focus of attention in the field of optical materials. In this work, we synthesized two birefringent crystals, C₂H₁₂N₆C₄O₄·2H₂O and Na₂C₄O₄·3H₂O, containing planar π-conjugated [C₄O₄]^2– groups. Attributed to the large structural anisotropy and relatively ordered arrangement of the [C₄O₄]^2– groups, C₂H₁₂N₆C₄O₄·2H₂O and Na₂C₄O₄·3H₂O possess large birefringence of 0.20–0.21 at 1064 nm. Meanwhile, they exhibit short ultraviolet cutoff edges at about 280–300 nm, corresponding to the large band gaps of 4.35 and 4.24 eV, respectively. Using structural analysis and first-principles calculations, the origins of such large birefringence are investigated and discussed. This work provides two potential UV birefringent crystals and prompts the search for novel birefringent materials.