Tetrahedral gold(I) clusters and related coinage metal clusters stabilized by boranylethynyl ligands

硬币金属的炔基配合物表现出广泛的结构变化，这是由炔基配体决定的，并由弱金属∙∙∙金属键扩展。我们已经证明了闭合十二硼乙炔的金(I)和银(I)络合物及其相关的硼乙炔配体是可获得的。这些配合物表现出极高的化学、热稳定性和光化学稳定性，并显示出良好的光致发光性能。双核膦金(I)络合物是容易合成的化合物的例子。这类与立体结构要求不高的膦配体的络合物完全基于分子间的自亲性相互作用进行二聚，得到四核金(I)簇合物。这些四核金(I)团簇在固态和溶液中都是稳定的，这为实验研究分子间亲金属相互作用提供了难得的可能性。这一提议的一个目标是合成、光物理表征和评价这类进一步的金簇合物与选定的硼乙炔配体以及由其他铸币金属组成的簇合物的亲金属相互作用。具有吡啶和膦配体的银(I)簇和配合物是碳基-闭合十二硼乙炔配体的不寻常配位性质的又一例子。较短的金属-金属距离表明有很强的亲金属相互作用。银(I)团簇表现出意想不到的室温磷光，其中一个团簇显示出这类化合物前所未有的磷光量子产率。因此，基于硼乙炔的银(I)、铜(I)络合物和簇合物的合成和光物理表征以及通过亲金属作用稳定的进一步的配体是另一个目标。作为前期工作的继续，含硼乙炔配体的混合硬币金属络合物的研究也是本研究的一部分。

Alkynyl complexes of the coinage metals exhibit a broad structural variety, which is decisively determined by the alkynyl ligands and expanded by weak metal∙∙∙metal bonds. We have shown that gold(I) and silver(I) complexes of carba-closo-dodecaboranylethynyl and related boranylethynyl ligands are accessible. These complexes exhibit unusually high chemical, thermal, and photochemical stabilities and they show promising photoluminescence. Dinuclear phosphane gold(I) complexes are examples for compounds that can be easily synthesized. Such complexes with sterically non-demanding phosphane ligands dimerize to give tetranuclear gold(I) clusters solely based on intermolecular aurophilic interactions. These tetranuclear gold(I) clusters are stable in the solid state and in solution, which provides the rare possibility to study intermolecular metallophilic interactions experimentally. The synthesis, photophysical characterization, and evaluation of metallophilic interactions of further gold clusters of this type with selected boranylethynyl ligands as well as clusters composed of the other coinage metals is one objective of this proposal. Silver(I) clusters and complexes with pyridine and phosphane ligands are a further example for the unusual coordination properties of the carba-closo-dodecaboranylethynyl ligand. Short metal-metal distances are indicative for strong metallophilic interactions. The silver(I) clusters exhibit unexpected room-temperature phosphorescence and one cluster shows an unprecedented phosphorescence quantum yield for this class of compounds. So, the synthesis and photophysical characterization of silver(I) as well as copper(I) complexes and clusters based on boranylethynyl and selected further ligands that are stabilized by metallophilic interactions is another objective. In continuation of our preliminary work, the study of mixed coinage metal complexes with boranylethynyl ligands is part of this study, as well.