Thioaluminogermanate M(AlS2)(GeS2)4 ( M = Na, Ag, Cu): Synthesis, Crystal Structures, Characterization, Ion-Exchange and Solid-State 27Al and 23Na NMR Spectroscopy

Fatimah Alahmari; Bambar Davaasuren; Abdul-Hamid Emwas; Alexander Rothenberger

doi:10.1021/acs.inorgchem.7b02980

Thioaluminogermanate M(AlS₂)(GeS₂)₄ ( M = Na, Ag, Cu): Synthesis, Crystal Structures, Characterization, Ion-Exchange and Solid-State ²⁷Al and ²³Na NMR Spectroscopy

Inorg Chem. 2018 Apr 2;57(7):3713-3719. doi: 10.1021/acs.inorgchem.7b02980. Epub 2018 Mar 14.

Authors

Fatimah Alahmari¹, Bambar Davaasuren, Abdul-Hamid Emwas, Alexander Rothenberger

Affiliation

¹ Institute for Research and Medical Consultations (IRMC) , Imam Abdulrahman bin Faisal University , Dammam 31441 , Kingdom of Saudi Arabia.

PMID: 29537828
DOI: 10.1021/acs.inorgchem.7b02980

Abstract

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).