Straightforward Route to the Adamantane Clusters [Sn4Q10]4- (Q = S, Se, Te) and Use in the Assembly of Open-Framework Chalcogenides (Me4N)2M[Sn4Se10] (M = MnII, FeII, CoII, ZnII) Including the First Telluride Member (Me4N)2Mn[Ge4Te10]

The reaction of K(2)Sn(2)Q(5) (Q = S, Se, Te) with stoichiometric amounts of alkyl-ammonium bromides R4NBr (R = methyl or ethyl) in ethylenediamine (en) afforded the corresponding salts (R4N)(4)[Sn(4)Q(10)] (Q = S, Se, Te) in high yield. Although the compound K2Sn2Te5 is not known, this reaction is also applicable to solids with a nominal composition K2Sn2Te5 which in the presence of R4NBr in en are quantitatively converted to the salts (R4N)(4)[Sn4Te10] on a multigram scale. These salts contain the molecular adamantane clusters [Sn(4)Q(10)](4-) and can serve as soluble precursors in simple metathesis reactions with transition metal salts to synthesize the large family of open-framework compounds (Me4N)(2)M[Sn4Se10] (M = Mn2+, Fe2+, Co2+, Zn2+). Full structural characterization of these materials as well as their magnetic and optical properties is reported. Depending on the transition metal in (Me4N)(2)M[Sn4Se10] the energy band gaps of these compounds lie in the range of 1.27-2.23 eV. (Me4N)(2)Mn[Ge4Te10] is the first telluride analogue to be reported in this family. This material is a narrow band gap semiconductor with an optical absorption energy of 0.69 eV. Ab initio electronic band structure calculations validate the semiconductor nature of these chalcogenides and indicate a nearly direct band gap.