Synthesis and characterization of metalloid gold clusters

目前的后续应用是基于DFG资助的结果，在该资助中，我们已经能够合成和表征许多新的金的金属簇合物。此外，我们能够对固体状态下团簇的协同性质有重要的了解，这一方面使电导率增加了两个数量级，另一方面对光学性质产生了影响。此外，我们还在另一个项目中建立了几组新的类金金属簇合物。目前正在继续进行这些研究，并计划在目前的申请中扩大到类金属银簇或类金属金银簇。这里我们可以求助于已经建立的Ag64(PnBu3)16Cl6的合成。该簇合物的稳定性应通过取代卤素取代基和在合成过程中引入金原子来增加。提高热稳定性和光化学稳定性对于该簇合物的进一步应用是至关重要的，该簇合物获得了约80%的优异结晶产率。类金属银团簇的合成也将进一步扩大，初步研究表明我们的合成方法具有潜力，在这种方法中，更大的类金属银团簇最高可达164？？银原子是可以接触到的。这些团簇与Ag64(PnBu3)16Cl6的敏感度和非球状结构相似，因此可以在这里建立一类新的类金属银团簇。在类金属金簇合物领域，我们的合成路线将扩展到硫酸盐稳定的簇合物。第一个例子表明，在这里，我们也可以打开一种新的类金属簇合物的途径，其中不存在主要基序，并且金原子在团簇核心中实现了新的排列。然后还可以解决主链对类金属金团簇的化学和物理性质有什么影响的问题，以及主链基序中没有包括在簇核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，其中一些计算是与美国费尔法克斯乔治梅森大学的克莱伯恩教授合作进行的。基于这些结果，可以更好地确定影响参数，从而可以更容易地计划合成，这也使计划的调查与应用相关的相关性变得清晰。

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.