Synthesis and Reactivity of Functionalized Binary and Ternary Thiometallate Complexes [(RT)4S6], [(RSn)3S4]2-, [(RT)2(CuPPh3)6S6], and [(RSn)6(OMe)6Cu2S6]4- (R = C2H4COOH, CMe2CH2COMe; T = Ge, Sn)

A series of compounds comprising functionalized thiometallate cages [(RT)(4)S-6] (R terminated by COO(H) or COR groups), based on adamantane (T=Ge) or double-decker (T = Sn) type structures or [(RSn)(3)S-4](2-) anionic defect heterocubanes were synthesized and their reactions with 1) transition-metal compounds and 2) hydrazine derivatives were explored. Hence it was possible to generate functionalized ternary CuSnS or CuGeS Clusters and to transfer COR ligands into CR(N-NH2) or CR(N-NHPh) terminal groups, respectively. The report provides the proof-of-principle for a directed functionalization and derivatization of chalcogenidometallate cages with respect to the formation of chalcogeniclometallate-organic hybrid compounds containing M/E semiconductor nodes, as an alternative to the so far most prominent M/O combination in metal-organic frameworks. DFT investigations deliver further insight in the peculiarities of Ge/S versus Sn/S precursors and their products.