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

造币金属的炔基配合物表现出广泛的结构多样性，这是由炔基配体决定性地决定的，并由弱金属∙∙金属键扩展。我们已经证明，金(I)和银(I)配合物的碳-接近十二硼乙基和相关的硼乙基配体是可接近的。这些配合物表现出异常高的化学、热和光化学稳定性，并表现出很有前途的光致发光。双核膦金(I)配合物是易于合成的化合物的例子。这种配合物与空间非要求膦配体二聚形成四核金(I)簇，仅基于分子间亲金相互作用。这些四核金簇在固态和溶液中都是稳定的，这为实验研究分子间亲金相互作用提供了难得的可能性。合成、光物理表征和评价这种类型的金团簇与选定的硼炔乙基配体以及由其他铸币金属组成的团簇的亲金相互作用是本提案的一个目标。与吡啶和膦配体的银(I)簇和配合物是碳-近十二硼酰乙基配体的不寻常配位性质的另一个例子。较短的金属-金属距离表明了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，其中一个团簇在这类化合物中表现出前所未有的磷光量子产率。因此，银(I)和铜(I)配合物的合成和光物理表征是另一个目标，这些配合物和团簇是基于硼基乙炔和选择的进一步通过亲金属相互作用稳定的配体。在我们前期工作的基础上，本研究还对硼基乙基配体的混合金属配合物进行了研究。

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.