簇基高核炔银簇化合物的合成与应用

Silver(I)-ethynide complexes have attracted great attention due to their structural variety and technological applications as precursors of non-linear optical materials, luminescence materials and rigid-rod molecular wires. In this proposal, we will employ metal-oxygen clusters as building blocks to react with silver(I)-ethynide complexes via self-assembly method to construct the cluster-based high-nuclearity silver(I)-ethynide cluster complexes. We will also focus our attention on their properties and applications, and try to explore and solve some of the basic problems existed in this field. First, we will synthesize various metal-oxygen clusters, namely lacunary polyoxometalates (POMs), phosphonate/arsonate-functionized POMs, POMs containing noble metal atoms, phosphonate/arsonate-functionized organotin oxo clusters and phosphonate/arsonate-functionized organoantimony oxo clusters, which react with silver(I)-ethynide complexes to construct the cluster-based high-nuclearity silver(I)-ethynide cluster compounds. Following this lead, we propose to synthesize a series of ethynyl-functionalized ligands, which are potentially useful in diverse areas such as optical materials and liquid crystalline materials. Furthermore, by making use of these high-nuclearity silver(I)-ethynide clusters, we will design and synthesize supramolecular hybrids based on polyoxometalates. The research results may provide the experimental and academic basis for the synthesis of excellent optical and liquid crystalline supramolecular hybrid materials.

炔银化合物以其结构多样性及在非线性光学材料、发光材料和分子线化合物的合成制备中的应用而引起人们广泛关注。本项目利用金属-氧簇为构筑基元，通过自组装等方法来构建簇基高核炔银簇，并研究其性质和应用，探索和解决其中的基本科学问题。首先，合成缺位、膦酸或胂酸修饰的、含有贵金属的无机金属-氧簇、膦酸或胂酸修饰的有机锡氧簇和有机锑氧簇，以这些金属-氧簇为构筑基元来构建簇基高核炔银簇化合物，并以此为基础设计不同功能的炔基配体，合成具有发光和液晶等性能的簇基炔银簇，进一步合成其超分子复合物，为合成具有优良的发光和液晶性能的超分子复合材料提供实验和理论基础。

高核炔银簇合物由于其结构的多样性和潜在的应用而引起人们广泛的兴趣。本项目采用钼多酸和钒多酸为模板，合成了两个高核炔银簇合物。另外，我们发现利用硫代磷酸盐与不同炔银的先驱体反应，得到了四种新颖的硫代磷酸盐配体修饰的银簇合物。这是首次由炔银配体和硫代磷酸盐配体共同来稳定簇合物，在簇的中心都存在一个模板离子（硫离子或银离子）。此外，我们还成功将膦酸配体引入到硫醇银体系的合成中。利用正丁基膦酸成功的合成了三个新颖的高核硫银簇，每一个簇合物都展现了三层核壳结构。这为利用膦酸或砷酸一类配体合成高核硫银簇开辟了一种新方法。