Creation of New Molecular Assemblies by Noncovalent Bonding Abilities of Thioamides

通过对大环聚内酰胺的硫代反应得到了新的大环聚硫内酰胺。化学转化增强了空穴中N-H质子的氢键结合能力，并提供了对氢受体如阴离子、酰胺和酯的强亲和力。用^1H NMR滴定法研究了大环受体的缔合性质。用X-射线单晶衍射法测定了包合物和[2]类轮烷的分子结构。研究了[2]类轮烷的穿线和脱线过程，并与1，3-苯二硫代酰胺进行邻位、邻位环化反应，得到κ^3S，C，S和κ^3S，N，S钳形配合物。配合物通过分子间N-H[三键]Cl氢键形成超分子网络。X-射线衍射分析表明，溶剂分子的存在有助于超分子网络的形成。该配合物在玻璃态和固态下都具有很强的发光。配合物的发射的衰减寿命是磷光发射的指示。在硫的存在下，二醛和二胺的Willgerodt-Kindler型反应容易地提供聚硫代酰胺。该聚合物不仅可以从水溶液中而且可以从有机溶液中有效地收集贵金属如Au（III）、Pt（IV）和Pd（II）。通过聚合物实现了从混合溶液中选择性吸附和分离第10族金属离子（Ni（II）、Pd（II）和Pt（IV））。模型配合物的分子结构表明，分子间的C=S[三键]M配位提供了选择性吸附性能。还展示了从合成有机液体废物中收集Au（III）。

Thionation of macrocyclic polylactams gave new macrocyclic polythiolactams. The chemical transformation enhanced hydrogen-bonding ability of the N-H protons in the cavity, and provided a strong affinity toward hydrogen-acceptors such as anions, amides, and esters. The association properties of the macrocyclic receptors were examined by ^1H NMR titration. The molecular structures of the inclusion complexes and [2]pseudorotaxanes were determined by X-ray crystallography. Threading and dethreading process of the [2]pseudorotaxanes was also been examined.Ortho, ortho-Cyclometalation of 1,3-benzenedicarbothioamides afforded κ^3S, C, S and κ^3S, N, S pincer complexes. The complexes formed supramolecular networks through intermolecular N-H【triple bond】Cl hydrogen bonds. X-ray crystallography revealed that the solvent molecules included in the crystal assisted formation of the supramolecular networks. The complexes exhibit strong emission on a glassy frozen state as well as in the solid state. The decay lifetime of the emission from the complexes is indicative of phosphorescent emission.Willgerodt-Kindler type reactions of dialdehydes and diamines in the presence of sulfur readily provided polythioamides. The polymers could effectively collect precious metals such as Au(III), Pt(IV), and Pd(II) from not only aqueous but also organic solutions. Selective adsorption and separation of group 10 metal ions (Ni(II), Pd(II), and Pt(IV)) from the mixture solutions were achieved by the polymers. The molecular structure of model complex revealed that intermolecular C=S【triple bond】M coordination afforded the selective adsorption properties. The collection of Au(III) from synthetic organic liquid waste was also demonstrated.