Preparation of Self-Assembled Monolayer Consisted of New Macrocyclic Ligands and Their Properties

我们通过钯催化的芳基胺化反应制备了新的大环配体氮杂杯吡啶。大环配体具有氮孤对电子，并在腔中提供供体位点。我们尝试了锌、铜离子与大环化合物的配位反应，并通过核磁共振谱和X射线晶体学对其结构进行了表征，同时通过硫代羰基化得到了一种新的大环聚硫代内酰胺。化学转化增强了空穴中N-H质子的氢键结合能力，并提供了对阴离子的强亲和力。用^1H NMR滴定法研究了聚硫内酰胺与阴离子的缔合性质。通过X射线衍射分析确定了大环主体化合物及其Cl^-配合物的分子结构，聚硫内酰胺具有4个位于空腔外侧的硫代羰基。我们尝试了在金电极上形成聚硫内酰胺的自组装单分子层（SAM）。聚硫内酰胺修饰电极的循环伏安图表明形成了共价硫-金属键和良好的包装单层的金电极上。表面增强拉曼光谱（Sers）也支持共价硫-金属键的形成。合成了由硫代酰胺基三齿配体构成的过渡金属配合物模型化合物，并通过X-射线结构分析确定了它们的分子结构。

We have prepared new macrocyclic ligands, azacalixpyridines, by Pd-catalyzed aryl amination. The macrocyclic ligands have nitrogen lone pair electrons and offer donor site in the cavity. We have attempted complexation of zinc and copper ions with the macrocycles, and the obtained inclusion complexes were characterized by NMR spectroscopy and X-ray crystallography.Thiocarbonylation of a macrocyclic tetralactam also gave a new macrocyclic polythiolactam. The chemical transformation enhanced hydrogen-bonding ability of the N-H protons in the cavity, and provided strong affinity toward anions. The association properties of the polythiolactam with anions was examined by ^1H NMR titration. The molecular structures of the macrocyclic host compound and its Cl^- complex were determined by X-ray structural analysis.The polythiolactam has four thiocarbonyl groups which are located on the outside of the cavity. We have attempted formation of self-assembled monolayer (SAM) of the polythiolactam on the gold electrode. Cyclic voltammograms of the polythiolactam modified electrodes indicated formation of a covalent sulfur-metal bond and well packed monolayer on the gold electrode. The covalent sulfur-metal bond formation was also supported by surface enhanced raman spectroscopy (SERS). The model transition-metal camplexes constituted of thioamide-based tridentate ligands have been prepared and their molecular structures were determined by x-ray structural analysis.