title: Understanding of multimetallic cluster growth.
abstract: The elucidation of formation mechanisms is mandatory for understanding and planning of synthetic routes. For (bio-)organic and organometallic compounds, this has long been realized even for very complicated molecules, whereas the formation of ligand-free inorganic molecules has widely remained a black box to date. This is due to poor structural relationships between reactants and products and the lack of structurally related intermediates--due to the comparably high coordination flexibility of involved atoms. Here we report on investigations of the stepwise formation of multimetallic clusters, based on a series of crystal structures and complementary quantum-chemical studies of (Ge2As2)(2-), (Ge7As2)(2-), [Ta@Ge6As4](3-), [Ta@Ge8As4](3-) and [Ta@Ge8As6](3-). The study makes use of efficient quantum-chemical tools, enabling the first detailed screening of the energy hypersurface along the formation of ligand-free inorganic species for a semi-quantitative picture. The results can be generalized for an entire family of multimetallic clusters.
authors.affiliation: Fachbereich Chemie and Wissenschaftliches Zentrum für Materialwissenschaften, Universität Marburg, Hans-Meerwein-Straße, D-35043 Marburg, Germany.
authors.forename: Stefan
authors.initials: S
authors.lastname: Mitzinger
authors.affiliation: Fachbereich Chemie and Wissenschaftliches Zentrum für Materialwissenschaften, Universität Marburg, Hans-Meerwein-Straße, D-35043 Marburg, Germany.|Institut für Nanotechnologie, Karlsruher Institut für Technologie, Hermann-von-Helmholtz Platz 1, D-76344 Eggenstein-Leopoldshafen, Germany.
authors.forename: Lies
authors.initials: L
authors.lastname: Broeckaert
authors.affiliation: Fachbereich Chemie and Wissenschaftliches Zentrum für Materialwissenschaften, Universität Marburg, Hans-Meerwein-Straße, D-35043 Marburg, Germany.
authors.forename: Werner
authors.initials: W
authors.lastname: Massa
authors.affiliation: Institut für Nanotechnologie, Karlsruher Institut für Technologie, Hermann-von-Helmholtz Platz 1, D-76344 Eggenstein-Leopoldshafen, Germany.
authors.forename: Florian
authors.initials: F
authors.lastname: Weigend
authors.affiliation: Fachbereich Chemie and Wissenschaftliches Zentrum für Materialwissenschaften, Universität Marburg, Hans-Meerwein-Straße, D-35043 Marburg, Germany.
authors.forename: Stefanie
authors.initials: S
authors.lastname: Dehnen