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

由硼基乙炔基配体稳定的四面体金（I）簇和相关造币金属簇

• 批准号: 228472253
• 负责人: Professor Dr. Maik Finze
• 金额: --
• 依托单位: Institut für Anorganische Chemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2012
• 资助国家: 德国
• 起止时间: 2011-12-31 至 2021-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/228472253?language=en
• 关键词: Tetrahedral; gold; clusters; related; coinage

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.

炔基配合物的钴金属表现出广泛的结构多样性，这是决定性的决定性的炔基配体和扩展的弱金属的钴金属键。我们已经表明，金（I）和银（I）配合物的carb-closo-dodecaboranylethynyl和相关的boranylethynyl配体是容易的。这些配合物表现出异常高的化学，热，和光化学稳定性，并显示出有前途的光致发光。双核膦金（I）配合物是可以容易地合成的化合物的实例。这种配合物与空间上不苛刻的膦配体二聚，得到四核金（I）簇完全基于分子间亲金相互作用。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。该建议的一个目标是进一步的金簇与选定的boranylethynyl配体以及簇组成的其他钴金属的亲金属相互作用的合成，物理表征和评价。银（I）簇和与吡啶和膦配体的配合物是碳-闭合-十二硼烷基乙炔基配体的不寻常配位性质的另一个例子。短的金属-金属距离指示强的亲金属相互作用。银（I）簇表现出意想不到的室温磷光，并且一个簇显示出这类化合物的前所未有的磷光量子产率。因此，另一个目的是合成和物理表征基于硼基乙炔基和通过亲金属相互作用稳定的所选择的其他配体的银（I）以及铜（I）络合物和簇。作为我们前期工作的延续，硼乙炔基配体与钴金属混合配合物的研究也是本研究的一部分。