Lanthanide−Transition Metal Chalcogenido Cluster Materials

[(THF)3Sm(SePh)2Zn(SePh)2]n decomposes to give a variety of products, including [(THF)8Sm4Se(SePh)8]2+[Zn8Se(SePh)16]2-, an ionic cluster that can also be prepared in more than 60% yield by stoichiometric addition of Se to a mixture of Sm(SePh)3 and Zn(SePh)2. The isostructural Nd compound [(THF)8Nd4Se(SePh)8]2+[Zn8Se(SePh)16]2- was also prepared by the stoichiometric route to establish the viability of this cluster type with redox-inactive Ln. In addition, the salt [Yb(THF)6]3+[Fe4Se4(SePh)4]3- was isolated and structurally characterized. These ionic cluster materials illustrate the difficulties associated with doping Ln ions into covalent metal chalcogenido matrixes.