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Thioaluminogermanate M(AlS 2 )(GeS 2 ) 4 ( M = Na, Ag, Cu): Synthesis, Crystal Structures, Characterization, Ion-Exchange and Solid-State 27 Al and 23 Na NMR Spectroscopy.

Inorganic Chemistry 2018 April 3
The new thioaluminogermanate Na(AlS2 )(GeS2 )4 (1) was successfully synthesized by a direct combination reaction. The compound crystallizes in the monoclinic space group P21 / n (no. 14) with unit cell parameters a = 6.803(3) Å, b = 38.207(2) Å, c = 6.947(4) Å, and β = 119.17(3)°. The crystal structure is composed of a [(AlS2 )(GeS2 )4 ]- 3D polyanionic network, in which Al and Ge atoms share the atomic positions and Na cations occupy the channels and voids formed by the connection of (Ge/Al)S4 tetrahedra. The title compound shows a cation-exchange property with monovalent Ag+ and Cu+ ions at room temperature in solvent media, resulting in the formation of the isostructural compounds Ag(AlS2 )(GeS2 )4 (2) and Cu(AlS2 )(GeS2 )4 (3), respectively. The ion-exchange products Ag(AlS2 )(GeS2 )4 (2) and Cu(AlS2 )(GeS2 )4 (3) show higher air stability and narrower bandgap energies compared to those of the parent compound Na(AlS2 )(GeS2 )4 (1).

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