title: 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).
abstract: A series of compounds comprising functionalized thiometallate cages [(RT)4S6] (R terminated by COO(H) or COR groups), based on adamantane (T=Ge) or double-decker (T=Sn) type structures or [(RSn)3S4]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 chalcogenidometallate-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.
authors.affiliation: Fachbereich Chemie and Wissenschaftliches Zentrum für Materialwissenschaften (WZMW), Philipps-Universität Marburg, Hans-Meerwein Strasse, 35043 Marburg, Germany.
authors.forename: Zohreh Hassanzadeh
authors.initials: ZH
authors.lastname: Fard
authors.forename: Lin
authors.initials: L
authors.lastname: Xiong
authors.forename: Christian
authors.initials: C
authors.lastname: Müller
authors.forename: Małgorzata
authors.initials: M
authors.lastname: Hołyńska
authors.forename: Stefanie
authors.initials: S
authors.lastname: Dehnen