Ba<sub>3</sub>Sb<sub>2</sub>(PO<sub>4</sub>)<sub>4</sub> and Cd<sub>3</sub>Sb<sub>2</sub>(PO<sub>4</sub>)<sub>4</sub>(H<sub>2</sub>O)<sub>2</sub>: Two New Antimonous Phosphates with Distinct\n[Sb(PO<sub>4</sub>)<sub>2</sub>] Structure Types and Enhanced Birefringence
Xiao-Bao Li (3824809)Chun-Li Hu (1397947)Fang Kong (1431676)Jiang-Gao Mao (1397944)
Abstract
Two new antimonous phosphates, namely\nBa<sub>3</sub>Sb<sub>2</sub>(PO<sub>4</sub>)<sub>4</sub> and Cd<sub>3</sub>Sb<sub>2</sub>(PO<sub>4</sub>)<sub>4</sub>(H<sub>2</sub>O)<sub>2</sub>, have been successfully\nprepared through mild hydrothermal reactions. Ba<sub>3</sub>Sb<sub>2</sub>(PO<sub>4</sub>)<sub>4</sub> features a 1D [Sb(PO<sub>4</sub>)<sub>2</sub>]<sup>3–</sup> chain structure separated by Ba<sup>2+</sup> cations while Cd<sub>3</sub>Sb<sub>2</sub>(PO<sub>4</sub>)<sub>4</sub>(H<sub>2</sub>O)<sub>2</sub> presents a 2D [Sb(PO<sub>4</sub>)<sub>2</sub>]<sup>3–</sup> layered structure with\nCd<sup>2+</sup> located at the interlayer space. The [Sb(PO<sub>4</sub>)<sub>2</sub>]<sup>3–</sup> chain in Ba<sub>3</sub>Sb<sub>2</sub>(PO<sub>4</sub>)<sub>4</sub> is the first example of 1D antimonous\nphosphate structure, and Cd<sub>3</sub>Sb<sub>2</sub>(PO<sub>4</sub>)<sub>4</sub>(H<sub>2</sub>O)<sub>2</sub> represents the first d<sup>10</sup> transition metal antimonous phosphate. Based on UV–vis–NIR\nspectra, both Ba<sub>3</sub>Sb<sub>2</sub>(PO<sub>4</sub>)<sub>4</sub> and Cd<sub>3</sub>Sb<sub>2</sub>(PO<sub>4</sub>)<sub>4</sub>(H<sub>2</sub>O)<sub>2</sub> can display large optical band gaps (4.30 and\n4.36 eV, respectively). But their transparent ranges are quite different\nbecause of the coordination water of Cd<sub>3</sub>Sb<sub>2</sub>(PO<sub>4</sub>)<sub>4</sub>(H<sub>2</sub>O)<sub>2</sub> (500–2000\nand 500–1300 nm for Ba and Cd compounds). The anhydrous Ba<sub>3</sub>Sb<sub>2</sub>(PO<sub>4</sub>)<sub>4</sub> shows high thermal\nstability in the nitrogen atmosphere (900 °C). Because of the\nincorporation of the lone pair cation of Sb(III), the birefringence\nof Ba<sub>3</sub>Sb<sub>2</sub>(PO<sub>4</sub>)<sub>4</sub> and Cd<sub>3</sub>Sb<sub>2</sub>(PO<sub>4</sub>)<sub>4</sub>(H<sub>2</sub>O)<sub>2</sub> has been enhanced to 0.086 and 0.053 at 532 nm, respectively.
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