Synthesis And Properties Of Tetrathiafulvalene Derivatives Containing Carboxylic Acid Groups

Tetrathiafulvalene（TTF）and its derivitives are star molecules and have been used in many areas,such as conductor,photoelectric materials and supramolecular chemistry system due to their electron-donor ability,redox properties,and their stable cations.As a good organic electron donor,TTF and its derivatives have great prospects in the preparation of multifunctional organic molecular materials.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:Novel supramolecular silver（I）complexes with EDT-TTF-4-py,L1,as the ligand,[Ag（L1）]₂（NO₃）₂（1）and[Ag（L1）₂]₃（CF₃SO₃）₄·2H₂O（2）were prepared by the self-assembly method.These two complexeswere characterized by elemental analysis,X-ray diffraction.In1,L1 acts as bis-bidentate ligand linking two silver ions through N and S atoms and forms a bimetallic macrocycle,and the bimetallic macrocycle is bridged by the weak Ag…O interactions to form a cyclic R₂²（14）supramolecular,resulting 1-dimensional loop chain along c axis.And there are S…S and C–H…O contacts between the loop chain.While in complex 2,two different types of Ag（L1）₂ cations are coordinated by the N_pyridine atom from L1 in a linear fashion and formed a trimer by weak Ag…Ag interaction.At room temperature,the electrical conductivity of complex 2 was 20 S·cm^-1 and showed a semi-conductive behavior,whereas complex 1 is an insulator.Structural analyses of these two complexes suggest that the interactions between the cation and anion play a significant role in stabilizing the structures,and also indicate that the frameworks and the electrical conductivity of the silver（I）complexes with TTF-py can be adjusted by variations counter anion.We successfully prepared four metal complexes[CoL2]·Bpy·2H₂O（1）,[CuL2]·Bpy（2）,[NiL2]·Bpy·2H₂O（3）,[ZnL2]·Bpy（4）,based on the double-p-thiobenzoic acid TTF-dithiomethyl derivative（ligand L2）.The single crystal structure of four kinds of complexes was obtained by single crystal diffractometry,and the structure was studied.At the same time,the microcrystalline electrodes of complexes 1,2 and 3 were prepared on the basis of their CV and photocurrent properties.The behavior in the photo-responsive phenomenon shows that metal coordination affects the electrochemical properties of the ligand.Finally,the potential applications of such organic-inorganic hybrid molecular systems in the application of photoelectrode materials were briefly explored.We successfully synthesized two types of TTF carboxylic acid derivatives,namely p-2-benzoic acid-TTF derivative（compound 4）,pyridine-TTF-benzoic acid derivative py-TTF-ph-COOH（compound 6）,by the literature review and experimental exploration.It was proved that the structure by NMR-H and HRMS.Finally,using electrochemical study of its redox properties...