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

组成复杂的无机结构单元的无机-有机杂化化合物和网络，如硫代金属簇合物，被认为是经典金属有机杂化化合物和网络的有价值的扩展，因为无机部分强烈地影响着各个相的物理化学性质。基于上一个项目DE-758/11-1的巨大成功，并在知名期刊上发表了14篇论文，我们想继续和扩大我们对功能化二元和三元硫属金属-有机杂化化合物和网络的研究，从而集中在两个选定的领域：a)用N供体螯合配体修饰硫属金属-有机杂化化合物用于(氧化还原活性)过渡金属离子的固存；b)定向通过2，3或4重共价有机键或通过更多的金属离子配位形成硫属金属-有机网络。为此，R*T/E笼(R*=官能化有机基团，T/E=14/16族元素)表面有机官能团的多样性将进一步变化，以增强后续反应的多样性。在杂化化合物中引入M/R*T/E三元团簇(M=过渡金属)的方法不同。将通过应用所有可用的实验方法和量子化学研究来探索所有反应产物的形成途径、稳定性以及化学和物理性质。除了对新化合物的表征外，这还将用于判断它们在分子捕获、键激活和氧化还原性质方面的反应性。将高度复杂的合成与多方面分析相结合在过去已被证明是有价值的，因此很可能在项目的继续和扩大方面发挥很好的作用。

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.