Structure And Property Of Tetrathiafulvalene Compound With Bicarboxylate

Tetrathiafulvalene （TTF） derivatives have been one kind of extensively studied functional molecules due to their applications in the field of material chemistry and supramolecular chemistry. Most current researches are about bifunctional TTF derivatives with good coordination ability. They can coordinate with a variety of metals to form coordination compounds, which are further assembled to different structures by hydrogen bonds short contacts. However,the study of TTF–carboxylate derivatives is relatively less. In this thesis, we pay attention to the complexes of TTF–carboxylate derivatives. The major contents we researched were as follows:1、In introduction, the important achievements of TTF derivatives are reviewed briefly, and then the new progresses of TTF derivatives in molecular recognition are illustrated. On the other hand, the different coordination modes of carboxyl groups are summarized and the recent researches on TTF–carboxylates are also described.2、TTF-dicarboxylate salts (C₁₀H₆O₄S₆Na₂·3H₂O) and their metal complexes with Ca（II） and Mg（II） were synthesized. Structures of complexes CaL₂（DMF）₂ and [Na₂（DMF）₂（H₂O）₉] [MgL₂（DMF）₂] were determined by single crystal X-ray diffraction. Equilibriums of the metal coordination, acid dissociation and electrochemistry have been studied to understand the charge transfer between metal cations and TTF group.3、Polymeric transition metal complexes of TTF-bicarboxylate ligand [CuL（2,2–bipy）_]n , [MnL（2,2–bipy）]_n , [MnL（4,4–bipy）（H₂O）]_n·CH₃CN and [ZnL（4,4–bipy）（H₂O）]_n·CH₃CN were synthesized and structures of these complexes were determined by single crystal X-ray diffraction. The results showed that they are one-dimensional or two-dimensional coordination polymers. Except acting as a rigid spacer, the TTF moiety is also a redox switchable building block. Antiferromagnetic and electrochemical properties of these complexes have been studied.