Different Chemical Environments of [GeSe] in the Li Compounds [Li(HO)][GeSe]·4.33HO, [{Li(thf)}GeSe], and [Li(HO)][MnGeSe], and Ionic Conductivity of Underlying "LiGeSe".

The crystalline selenido germanates [Li(HO)][GeSe]·4.3HO (), [{Li(thf)}GeSe] (), and [Li(HO)][MnGeSe] () (thf = THF = tetrahydrofuran) were obtained by an extraction of a glassy ternary phase of the nominal composition LiGeSe (=LiS·2GeSe) with water () or THF () and slow evaporation of the solvent or by being layered with MnBr in HO/MeOH (), respectively. The compounds contain known selenido germanate anions, however, for the first time with Li counterions. This is especially remarkable for the prominent {[MnGeSe]} open-framework structure, which was reported to crystallize with (NMe), Cs, Rb, and K counterions, but it has not yet been realized with the smallest alkali metal cation. Impedance spectroscopic studies on LiGeSe classify the glassy solid as a moderate Li ion conductor.