Ba 3 Sb 2 (PO 4 ) 4 and Cd 3 Sb 2 (PO 4 ) 4 (H 2 O) 2 : Two New Antimonous Phosphates with Distinct [Sb(PO 4 ) 2 ] Structure Types and Enhanced Birefringence

作者：Xiaobao Li, Chun‐Li Hu, Fang Kong, Jiang‐Gao Mao · 发表于：Inorganic Chemistry · 年份：2021 · DOI：10.1021/acs.inorgchem.0c03419 · 被引用次数：36 · 研究领域：Crystal Structures and Properties、Nuclear materials and radiation effects、Luminescence Properties of Advanced Materials

Two new antimonous phosphates, namely Ba 3 Sb 2 (PO 4 ) 4 and Cd 3 Sb 2 (PO 4 ) 4 (H 2 O) 2, have been successfully prepared through mild hydrothermal reactions. Ba 3 Sb 2 (PO 4 ) 4 features a 1D [Sb(PO 4 ) 2 ] 3– chain structure separated by Ba 2+ cations while Cd 3 Sb 2 (PO 4 ) 4 (H 2 O) 2 presents a 2D [Sb(PO 4 ) 2 ] 3– layered structure with Cd 2+ located at the interlayer space. The [Sb(PO 4 ) 2 ] 3– chain in Ba 3 Sb 2 (PO 4 ) 4 is the first example of 1D antimonous phosphate structure, and Cd 3 Sb 2 (PO 4 ) 4 (H 2 O) 2 represents the first d 10 transition metal antimonous phosphate. Based on UV–vis–NIR spectra, both Ba 3 Sb 2 (PO 4 ) 4 and Cd 3 Sb 2 (PO 4 ) 4 (H 2 O) 2 can display large optical band gaps (4.30 and 4.36 eV, respectively). But their transparent ranges are quite different because of the coordination water of Cd 3 Sb 2 (PO 4 ) 4 (H 2 O) 2 (500–2000 and 500–1300 nm for Ba and Cd compounds). The anhydrous Ba 3 Sb 2 (PO 4 ) 4 shows high thermal stability in the nitrogen atmosphere (900 °C). Because of the incorporation of the lone pair cation of Sb(III), the birefringence of Ba 3 Sb 2 (PO 4 ) 4 and Cd 3 Sb 2 (PO 4 ) 4 (H 2 O) 2 has been enhanced to 0.086 and 0.053 at 532 nm, respectively.