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Birefringent crystals are very important optical materials, which are widely used in the fields of optics and communication. In this work, we reported a new iodate, NaGaIOF, synthesized by mild hydrothermal method. NaGaIOF crystallized in the monoclinic space group P2/c (No. 14) and it featured a novel [Ga(IOF)(IO)] layer stacked with Na cations located in the void maintaining charge balance. Notably, IO and IOF anionic units appeared in the same time in the A-Ga-I-O/F (A = alkali metal) system. According to the experimental characterization and theoretical calculations, NaGaIOF showed a wide bandgap (4.27 eV) and large birefringence (Δn∼ 0.203, Δn = 0.197 at 1064 nm), indicating its potential use as a birefringent material.
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