Multi-Valent Group 14 Chalcogenide Architectures from Ionic Liquids: 0D-{[Cs@SnII4 (GeIV4 Se10 )4 ]7- } and 2D-{[SnII (GeIV4 Se10 )]2- }.

In order to explore if and how salts comprising polycations and salts comprising polyanions might interact, the [AlBr4 ]- salt of the [Pt@Bi10 ]4+ cluster cation was added to the reaction mixture for the synthesis of the supersphere cluster anion [Ge24 Sn36 Se132 ]24- from Cs4 [Ge4 Se10 ]⋅H2 O and SnCl4 ⋅5 H2 O under ionothermal conditions at 120 °C. Indeed, the reaction yields two new compounds, depending on the cation of the used ionic liquid. Apparently, the polycation is not retained under the given conditions, but it acts as a reductant affording SnII . In a (C4 C1 C1 im)+ -based ionic liquid mixture, a unique supertetrahedral anion is obtained that embeds a Cs+ cation, 0D-{[Cs@SnII4 (GeIV4 Se10 )4 ]7- }, while (C4 C1 im)+ cations stabilize an unprecedented ternary layered anion, 2D-{[SnII (GeIV4 Se10 )]2- }. Test reactions with common sources of SnII did not afford the new compounds, indicating the necessity of an in situ reduction, for which the polycation seems appropriate.