Synthesis And Properties Of Sulfur–Rich Compounds With Amide Groups

Tetrathiafulvalene （TTF） and its derivatives, being widely used in material chemistryand supramolecular chemistry, have stimulated great interest for a long time, due to theirunique donor and redox properties. The amide groups can form rich hydrogen–bonds,which make them have good application in molecular assembling and responding.Although some crystal structures of TTF–amide derivatives have been reported, theirproperties need to be further explored. In this thesis, we pay attention to the study on akind of new bifunctional TTF derivative with dioxotetraamine and a new TTF basedorganogel. The major contents we researched were as follows:In introduction, the properties and important achievements of TTF derivatives arereviewed briefly. Recent researches on TTF–amide and dioxotetraamine（diamino–diimido） ligands are summarized. Especially, the new researches on molecularrecognition of these compounds are described.Besides, TTF based organogels containingamide moiety are also reviewed.In chapter2, TTF–（CONHCH₂CH₂NH₂）₄（L） and the complexes of L with Ni（II）、Cu（II） were synthesized. The crystal structures of the Ni（II） complexes were determinedby single crystal X–ray diffraction. Equilibriums of proton transition and metalcoordination for this ligand have been studied by means of pH titration. The responses ofpH and metal ion coordination to the redox state of the ligand are also discussed.In chapter3, supramolecular compounds of protonated HL with SO₄^2-anions weresynthesized. Crystal structure analysis showed that there are lots of hydrogen bonds inthe structures of the complex. Redox recognitions of HL to anions and cations wereinvestigated by CV method. The results indicate that the stronger the hydrogen bonds between anions and–CONH groups are, the larger the potential shifts are.In chapter4, a new TTF based low-molecular-weight-gelators（LMWG1） containingamide moiety and long alkyl chains were synthesized, and the gelation ability ofLMWG1was tested in several solvents. The gels were investigated with SEM and TEM.Finally, the electrochemical properties of LMWG1were also investigated by CV method.