Journal
INORGANIC CHEMISTRY
Volume 56, Issue 2, Pages 962-973Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.6b02667
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Funding
- NSF of China [91222204, 21403231, 21303203, 21403237, 21401052]
- NSF of Fujian Province [2014J05025, 2014J05034]
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Quaternary metal thiophosphates containing second-order Jahn-Teller distorted d(10) Ag+ and lone-pair cations, Ag3Bi(PS4)(2) (1), Ag7Sn(PS4)(3) (2), and Ag7Pb(PS4)(3) (3), were obtained by solid-state synthesis. The structural frameworks of 2 and 3 feature an infinite 1-D interchiral double helix(infinity)(1)Ag(3)P(2)S(11)), which is rare in inorganic compounds. Compound 3 undergoes a significant first-order structural phase transition from monoclinic to hexagonal at similar to 204 degrees C. This can be ascribed to the significant mismatch in the expansion coefficients between Pb-S (Ag-S) and P-S bonds evaluated by bond valence theory. The three compounds are Ag+ ionic conductors, and Ag+ ion migration pathways are proposed by calculating maps of low bond valence mismatch. Moreover, the optical properties of the three compounds were studied, and electronic structure calculations were performed. The combination of second-order Jahn-Teller distorted d(10) cation and lone -pair cation provides a new strategy to explore new metal thiophosphates with interesting structures and promising properties.
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