Na[B3IO7(OH)] and Na2[B4IO9](IO3): Explorations of Boroiodates with Strong Second Harmonic Generation Response and Large Birefringence

In the exploration of nonlinear optical (NLO) materials, developing new functional groups for high performance is essential. Achieving a balance among band gap, second harmonic generation (SHG), and birefringence within a compound is quite challenging. By directly connecting iodates and borates by B-O-I bridges, two boroiodates with novel [B3IO8(OH)]3- and [B4IO11]5- anionic functional groups, namely, Na[B3IO7(OH)] (NBIO-I) and Na2[B4IO9](IO3) (NBIO-II), were successfully synthesized for the first time through the boric acid melting method under different molar ratios of H3BO3/NaIO3. NBIO-I (Pbca) features a unique 1D infinity 1[B3IO7(OH)]- chain composed of corner-sharing [B3O6(OH)]4- groups with [IO3]- groups hanging on both sides of the chain. In contrast, NBIO-II (Cc) displays a novel 2D layer of infinity 2[B4IO9]-, in which all of the [IO3]- groups are hanging on the same side of the infinity 2[B4O7]2- layer formed by corner-sharing [B3O7]5- and [BO3]3- groups. Remarkably, NBIO-II exhibits a wide band gap (4.3 eV), large birefringence (0.298@546 nm), and strongest SHG response (7.8 x KDP) among borate-iodates reported previously. This work not only discovered NBIO-II as promising NLO crystals but also provided an effective synthetic route for new boroiodates with excellent optical properties.