Creation of New Molecular Assemblies by Noncovalent Bonding Abilities of Thioamides

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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.