Syntheses And Property Of Sulfur-rich Compounds With Carboxylate Groups

Tetrathiafulvalene （TTF） derivatives have been one kind of extensively studiedfunctional molecules due to their applications in the field of material chemistry andsupramolecular chemistry. On the other hand, carboxylates have been used in analysischemistry, chemical catalysis, bionic chemistry, and material chemistry. In this thesis,we pay attention to the study of TTF-carboxylate derivatives. The major contents weresearched were as follows:1、In introduction, the important achievements of TTF derivatives are reviewedbriefly. On the other hand, the different coordination modes of carboxyl groups aresummarized and the recent researches on TTF–carboxylates are also described.2、TTF-dicarboxylate salts (C₁₀H₆O₄S₆Na₂·3H₂O) and their metal complexes withMg（II） and Zn（II） were synthesized. Structures of complexes[Mg（HL）（phen）（H₂O）₃]·HL·phen and [Zn₂L₂（phen）₂（H₂O）₂] were determined by singlecrystal X-ray diffraction. Equilibrium of electrochemistry has been studied tounderstand the charge transfer between metal cations and TTF group.3、 Polymeric transition metal complexes with Cd（II） and Mn（II） ofTTF-dicarboxylate ligand,[CdL（bpy）],[CdL（dpypn）] and [MnL（dpypn）], weresynthesized under solvothermal conditions. The structures of these complexes weredetermined by single crystal X-ray diffraction. The results showed that they areone-dimensional or two-dimensional coordination polymers. Except acting as a rigidspacer, the TTF moiety is also a redox switchable building block that can buildpolymeric metal complexes and metal-organic framework with redox activities.4、The TTF-dicarboxylate acid (C₁₀H₈O₄S₆) is synthesized, and the redoxproperty of the acid is researched by UV-vis-NIR spectra and electrochemistry. The equilibriums of DMTTTF（COOH）₂with the added small N-heterocycle molecules arediscussed.