Synthesis and characterization of metalloid gold clusters

类金属金团簇的合成与表征

• 批准号: 434242866
• 负责人: Professor Dr. Andreas Schnepf
• 金额: --
• 依托单位: Institut für Anorganische Chemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 资助国家: 德国
• 项目状态: 未结题
• 来源: https://gepris.dfg.de/gepris/projekt/434242866?language=en
• 关键词: Synthesis; characterization; metalloid; gold; clusters

The present follow-up application is based on the results of a DFG grant, in which we have already been able to synthesize and characterize many new metalloid cluster compounds of gold. Furthermore, we were able to gain important insights into the cooperative properties of the clusters in the solid state, which on the one hand increase the electrical conductivity by two orders of magnitude and have on the other hand an impact on the optical properties. Furthermore, we were able to establish several new groups of metalloid cluster compounds of gold in another project. These investigations are now to be continued, with an extension to metalloid silver clusters or intermetalloid gold/silver clusters being planned in the current application. Here we can fall back on the already established synthesis of Ag64(PnBu3)16Cl6. The stability of this cluster should be increased by substitution of the halogen substituents and by the incorporation of gold atoms during synthesis. Increasing the thermal and photochemical stability is essential for further applications of this cluster, which is obtained in excellent crystalline yields of about 80%. The synthesis of metalloid silver clusters is also to be further expanded, with initial investigations showing the potential of our synthetic approach, in which significantly larger metalloid silver clusters with up to 164 ?? silver atoms are accessible. These clusters are like Ag64(PnBu3)16Cl6 in terms of both sensitivity and the unusual non-spherical structure, so that a new class of metalloid silver clusters can be established here. In the field of metalloid gold clusters, our synthesis route is to be extended to thiolate-stabilized clusters. A first example shows that here too we can open-up access to a new class of metalloid cluster compounds in which no staple motifs are present and where new arrangements of the gold atoms are realized in the cluster core. The question what influence the staple motifs on the chemical and physical properties of a metalloid gold cluster have can then also be addressed and whether the gold atoms in the staple motif, which are not included in the cluster core can be used for applications, e.g. in the field of catalysis. These investigations are supported by quantum chemical calculations, some of which are carried out in collaboration with Prof. Clayborne at George Mason University, Fairfax/USA. Based on these results, influencing parameters can be better identified, which makes it possible to plan synthesis more easily, which also makes the application-related relevance of the planned investigations clear.

目前的后续申请是基于DFG资助的结果，其中我们已经能够合成和表征许多新的金类金属簇化合物。此外，我们能够对固态团簇的合作性质获得重要的见解，这一方面增加了两个数量级的电导率，另一方面影响了光学性质。此外，我们还在另一个项目中建立了几个新的金类金属团簇化合物。这些调查现在将继续进行，目前的应用计划扩大到类金属银团簇或类金属间金/银团簇。在这里，我们可以回到已经建立的Ag64(PnBu3)16Cl6的合成。在合成过程中，通过卤素取代基的取代和金原子的掺入，可以提高团簇的稳定性。提高热和光化学稳定性对该簇的进一步应用至关重要，该簇的结晶率约为80%。类金属银团簇的合成也将进一步扩大，初步研究显示了我们的合成方法的潜力，其中更大的类金属银团簇高达164 ?？银原子是可以接触到的。这些团簇在灵敏度和不寻常的非球形结构方面都与Ag64(PnBu3)16Cl6相似，因此可以在这里建立一类新的类金属银团簇。在类金属金团簇领域，我们的合成路线将扩展到硫代酸稳定的团簇。第一个例子表明，在这里，我们也可以打开通往一类新的类金属簇化合物的通道，在这种化合物中不存在主基序，并且在簇核中实现了金原子的新排列。短钉基序对类金属金团簇的化学和物理性质有什么影响，以及短钉基序中不包括在团簇核心中的金原子是否可以用于应用，例如在催化领域。这些研究得到了量子化学计算的支持，其中一些是与美国乔治梅森大学的Clayborne教授合作进行的。基于这些结果，可以更好地识别影响参数，从而可以更容易地进行计划综合，也使计划调查的应用相关性更加明确。