Four New Sb‐based Orthophosphates: Cation Regulation to Investigate Diversified Structural Architecture

• Published in: Chemistry : a European journal 2023-06, Vol.29 (34), p.e202300626-n/a
• Main Authors: Huang, Hongyu, Li, Na, Zhang, Ruixin, Wang, Xinmei, He, Xianmeng, Wu, Lei, Liu, Lili, Jing, Qun, Chen, Zhaohui
• Format: Article
• Language: English
• Subjects: Alkali metals; cation regulation; Chemistry; Density functional theory; electronic band structure; Energy bands; Lamellar structure; Optical properties; Orthophosphates; Phosphates; Sb-based orthophosphates; structural dimension; structure evolution
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.202300626

In the work, four new Sb‐based phosphates, K4(SbO2)5(PO4)3, Rb(SbO2)2PO4, Rb3(SbO2)3(PO4)2 and Cs3(SbO2)3(PO4)2(H2O)1.32, were successfully synthesized by a high‐temperature melt method. Among them, Rb(SbO2)2PO4 and Rb3(SbO2)3(PO4)2 are the first reported examples of Rb‐containing alkali metal Sb‐based phosphates. They show three‐dimensional (3D) frameworks composed of [Sb8P4O30]∞ layer for K4(SbO2)5(PO4)3 and [Sb6P2O20]∞ layer for Rb(SbO2)2PO4, and 2D lamellar structure composed of [Sb3P2O10]∞ for Rb3(SbO2)3(PO4)2 and Cs3(SbO2)3(PO4)2(H2O)1.32. A detailed structural comparison shows that the structure dimensions for them transfer from 1D to complex 3D framework with the increase of (Sb+P)/O ratio, which affects performances of the compounds. Optical property and energy band structure calculations were also carried out based on the density functional theory (DFT). The present study enriches the diversity of Sb‐based phosphates and paves the way for further explore their optical properties in the future. Two cases of Rb‐containing Sb‐based phosphates were discovered for the first time and the abundant coordination of Sb atoms can effectively regulate the skeleton to produce novel anionic groups, which can greatly enrich the structural chemistry and practical properties of phosphates.