Multi‐Valent Group 14 Chalcogenide Architectures from Ionic Liquids: 0D‐{[Cs@Sn^II₄(Ge^IV₄Se₁₀)₄]⁷⁻} and 2D‐{[Sn^II(Ge^IV₄Se₁₀)]²⁻}

Abstract

Abstract In order to explore if and how salts comprising polycations and salts comprising polyanions might interact, the [AlBr 4 ] − salt of the [Pt@Bi 10 ] 4+ cluster cation was added to the reaction mixture for the synthesis of the supersphere cluster anion [Ge 24 Sn 36 Se 132 ] 24− from Cs 4 [Ge 4 Se 10 ] ⋅ H 2 O and SnCl 4 ⋅ 5 H 2 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 Sn II . In a (C 4 C 1 C 1 im) + ‐based ionic liquid mixture, a unique supertetrahedral anion is obtained that embeds a Cs + cation, 0D‐{[Cs@Sn II 4 (Ge IV 4 Se 10 ) 4 ] 7− }, while (C 4 C 1 im) + cations stabilize an unprecedented ternary layered anion, 2D‐{[Sn II (Ge IV 4 Se 10 )] 2− }. Test reactions with common sources of Sn II did not afford the new compounds, indicating the necessity of an in situ reduction, for which the polycation seems appropriate.