Assembly of coordination polymers from polythioethers with conjugated backbones



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The syntheses, structures and electronic properties of a new class of polythioethers with conjugated backbones and their transition metal complexes are reported. Hexakis(phenylthio)-1,5-hexadien-3-yne and hexakis(isopropylthio)- 1,5-hexadien-3-yne have been synthesized and their molecular structures determined by X-ray crystallography. These compounds exhibited photoluminescence in the solid state. The self-assembly of coordination networks from reactions of these ligands with silver(I) salts is described. These coordination polymers exhibited photoluminescence in the solid state and were characterized by X-ray analysis. The electrochemical properties of these ligands and their silver(I) coordination polymers were studied by cyclic voltammetry. Octakis(methylthio)-1,3,5-hexatriene, octakis(benzylthio)-1,3,5-hexatriene and hexakis(phenylthio)-1,3-butadiene have been prepared and their molecular structures determined by X-ray crystallography. The self-assembly of the coordination polymer from the reaction of octakis(methylthio)-1,3,5-hexatriene with silver(I) nitrate is described. Polythioethers with these conjugated backbones described react as bisbidentate ligands with palladium(II) to yield dinuclear palladium complexes. Mononuclear palladium(II) and platinum(II) complexes of such ligands have also been prepared. The structures of these mononuclear and bimetallic complexes were determined by X-ray analysis. The synthesis and crystal structure of the dinuclear ruthenium(II) complex of octakis(methylthio)-1,3,5-hexatriene is also reported.