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

我们用pd催化芳基胺化法制备了新的大环配体，偶氮卡羟基吡啶。大环配体具有氮孤对电子，在腔内提供给体位。我们尝试了锌和铜离子与大环的络合，并用核磁共振波谱和x射线晶体学对所得到的包合物进行了表征。大环四内酯的硫羰基化也得到了新的大环聚硫内酯。化学转化增强了腔内N-H质子的氢键能力，并对阴离子具有较强的亲和力。采用^1H核磁共振滴定法研究了聚硫内酰胺与阴离子的缔合性质。通过x射线结构分析确定了大环主体化合物及其Cl^-配合物的分子结构。所述聚硫内酰胺具有位于所述空腔外部的四个硫羰基。我们尝试在金电极上形成聚硫内酰胺的自组装单层（SAM）。聚硫内酰胺修饰电极的循环伏安图表明在金电极上形成了共价硫-金属键和良好的单层。表面增强拉曼光谱（SERS）也支持了共价硫-金属键的形成。制备了由硫酰胺基三齿配体构成的模型过渡金属络合物，并用x射线结构分析确定了其分子结构。

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.