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Abstract:
In order to explore if and how salts comprising polycations and salts comprising polyanions might interact, the [AlBr4](-) salt of the [Pt@Bi-10](4+) cluster cation was added to the reaction mixture for the synthesis of the supersphere cluster anion [Ge24Sn36Se132](24-) from Cs-4[Ge4Se10]center dot H2O and SnCl4 center dot 5H(2)O under ionothermal conditions at 120 degrees 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-4(II)((Ge4Se10)-Se-IV)(4)](7-)}, while (C(4)C(1)im)(+) cations stabilize an unprecedented ternary layered anion, 2D-{[Sn-II((Ge4Se10)-Se-IV)](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.
