Chalcogenidometallate-Organic Hybrid Compounds and Networks: Experimental and Theoretical Studies on Syntheses and Reactivity

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Inorganic-organic hybrid compounds and networks that comprise complex inorganic building units, such as chalcogenidometallate clusters, are considered valuable extensions of the classical metalorganic hybrid compounds and networks, since the inorganic part strongly affects the physico-chemical properties of the respective phases. Based on the large success of the previous project DE-758/11-1, that gave rise to 14 publications in reputable journals, we would like to continue and extend our investigations on functionalized binary and ternary chalcogenidometallate-organic hybrid compounds and networks, thereby focusing on two selected areas: A) decoration of the chalcogenidometallate-organic hybrid compounds with N donor chelating ligands for (redox-active) transition metal ion sequestration; B) directed formation of chalcogenidometallate-organic networks via 2, 3, or 4-fold covalent organic linkage or via coordination of additional metal ions. For this, the variety of the organic functionalities on the surfaces of binary R*T/E cages (R* = functionalized organic group, T/E = group 14/16 elements) will be further varied to enhance the variety of subsequent reactions. The incorporation of ternary M/R*T/E clusters (M = transition metal) into the hybrid compounds will be approached following different ways. Formation pathways, stabilities, as well as chemical and physical properties of all reaction products will be explored by application of all available experimental methods and by means of quantum chemical studies. Besides characterization of the novel compounds, this shall serve to judge on their reactivity regarding molecular trapping, bond activation and redox properties. The combination of high-sophisticated syntheses with multi-faceted analyses has proved of value in the past and will therefore be likely to work finely at the continuation and extension of the project.