Hydroxyl-Driven Enhanced Birefringence in Borophosphates

Borophosphates have become promising candidates for ultraviolet or deep-ultraviolet functional crystals. Through high-temperature solution method, four new borophosphates, K2B2P2O9, (NH4)2BP2O7(OH), K2BP2O7(OH), and P21/c-(NH4)2B2P3O11(OH), were acquired successfully. Single crystal X-ray diffraction suggests that K2B2P2O9, (NH4)2BP2O7(OH), and K2BP2O7(OH) belong to the noncentrosymmetric space group, while P21/c-(NH4)2B2P3O11(OH) belongs to the centrosymmetric compound. It is worth mentioning that K2B2P2O9, (NH4)2BP2O7(OH), and K2BP2O7(OH) present the new fundamental building blocks [B2P2O11], [BP2O10H], and [BP2O9(OH)], respectively, as far as we know. Compared with K2B2P2O9, (NH4)2BP2O7(OH), K2BP2O7(OH), and P21/c-(NH4)2B2P3O11(OH) exhibit a larger optical anisotropy, further confirming the positive effect of hydroxyl groups on birefringence. UV–vis–NIR diffuse reflectance spectra display that K2B2P2O9 and (NH4)2BP2O7(OH) have short UV cutoff edges. Meanwhile, theoretical calculations were conducted to comprehend their optical properties and electronic structures.