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

无机-有机杂化化合物和网络，包括复杂的无机结构单元，如硫族金属化物簇，被认为是经典的金属有机杂化化合物和网络的有价值的扩展，因为无机部分强烈影响相应相的物理化学性质。基于之前DE-758/11-1项目的巨大成功，在知名期刊上发表了14篇论文，我们希望继续并扩展我们对官能化二元和三元硫属元素化物-有机杂化化合物和网络的研究，从而专注于两个选定的领域：A）用N供体螯合配体修饰硫属元素化物-有机杂化化合物，（氧化还原活性的）过渡金属离子螯合; B）通过2、3或4-重共价有机键或通过配位另外的金属离子定向形成硫属元素化物-有机网络。为此，二元R*T/E笼（R* =官能化有机基团，T/E =第14/16族元素）表面上的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。将三元M/R*T/E簇合物（M =过渡金属）引入杂化化合物中将按照不同的方式进行。所有反应产物的形成途径、稳定性以及化学和物理性质将通过应用所有可用的实验方法和通过量子化学研究来探索。除了新化合物的表征外，这将用于判断它们在分子捕获、键活化和氧化还原性质方面的反应性。过去已经证明，将高度复杂的综合与多方面的分析相结合是有价值的，因此很可能在项目的继续和扩展方面发挥良好的作用。

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.