Abstract
Reaction of a mixture of CuCl, PhSnCl(3) and PEt(2)Ph with S(SiMe(3))(2) in THF resulted initially in the unexpected synthesis of the ionic, mixed copper-tin sulfide cluster [Li(thf)(4)][Cu(19)S(28)(SnPh)(12)(PEt(2)Ph)(3)] in low yields. However, by adding NBu(4)Cl to the reaction solutions we were able to selectively synthesize the structurally similar cluster ion in (NBu(4))[Cu(19)S(28)(SnPh)(12)(PEt(2)Ph)(3)]. Structural characterization by single crystal X-ray analysis reveals that the cluster anions consist in principle of a copper sulfide core decorated by PhSn(3+) groups. Although additional phosphine ligands are attached to copper atoms the clusters possess an open 'Cu(3)S(3)' face mostly protected by the [Li(thf)(4)](+) and (NBu(4))(+) counterions in the crystal structure. The cluster (NBu(4))[Cu(19)S(28)(SnPh)(12)(PEt(2)Ph)(3)] displays near-infrared, temperature-dependent photoluminescence at ∼820-930 nm in the solid state, which is especially bright at temperatures below ∼100 K.
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