A2BBi2(PO4)2(P2O7) (A = K, Rb, B = Pb, Cd): the Effect of Cation Sizes on Structural Evolution. Issue 42 (24th September 2020)

• Record Type: Journal Article
• Authors: Qi, Lu; Chen, Zhaohui; Li, Lu; Jing, Qun; Li, Na; Jiang, Zhongqi; Dong, Xiaoyu; Lee, Ming‐Hsien
• Is Part Of: European journal of inorganic chemistry. Issue 42(2020)
• Page Start: 4007
• Page End: 4014
• Publication Date: 2020-09-24
• Subjects: Mixed‐metal phosphates -- A‐site cations -- Difference‐value -- Theoretical calculations; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.202000716
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract : Two homologous new mixed‐metal phosphates K2 PbBi2 (PO4 )2 (P2 O7 ) (I ) and Rb2 CdBi2 (PO4 )2 (P2 O7 ) (II ) were successfully synthesized in A2 BBi2 (PO4 )2 (P2 O7 ) (A = K, Rb, B = Pb, Cd) system through the traditional high‐temperature solid‐phase method. The single crystal structures of the two compounds are shown to be the unique three‐dimensional (3D) framework composed of different types of layers, but not isomorphic. We compared series compounds A2 PbBi2 (PO4 )2 (P2 O7 ) (A = K, Rb, Cs), which are isomorphic and crystallize in the same space group Pnma . It is noteworthy that they are distinct different in degree of structural disorder, which is tuned by A‐site cations. The effect of A‐site cations is recognized by analyzing the disorder degree in three related structures and other available 182 mixed‐metal phosphates. To the best of our knowledge, such structural analysis is rarely reported in inorganic phosphates and the cation modulation strategy can be used to guide structural disorder according to the difference‐value (D‐value) of cation radii. Furthermore, the syntheses, thermal analysis, relevant spectroscopic measurements and theoretical calculations for I and II compounds were also discussed. Abstract : Two new mixed‐metal phosphates K2 PbBi2 (PO4 )2 (P2 O7 ) and Rb2 CdBi2 (PO4 )2 (P2 O7 ) were firstly reported and the cation size effect has substantial influence on the crystal structural disorder combining with the title compounds and 182 phosphates.