The Research Of Coordination Assembly And Properties Of Tetrathiafulvalene Dicarboxylate

Due to its unique electron-donating and electrochemical properties,tetrathiafulvalene(TTF)has been received wide attention and has potential applications in many areas,such as conductors,photoelectric materials,magnetic materials,and sensors.So far,the study of TTF and its derivatives has mainly been focused on the crystal structures of coordination complexes and organic semiconductor materials.However,using TTF-carboxylates as building blocks to form MOFs and charge transfer(CT)compounds has rarely been reported.In this thesis,by incorporating bispyridine derivatives and transition metal ions into TTF-carboxylates system,new MOFs and CT compounds with redox,structural confinement effects and photocurrent response properties were studied.The major contents are as follows:In introduction,the properties and research progress of TTF derivatives such as conductor,field-effect transistor,and sensors are mainly reviewed.Research progress on TTF-carboxylates in many applications are summarized.TTF-carboxylates and metal ions are linked via coordination bonds to form multi-dimensional extended structures and to build MOFs with redox properties.It can be used in many molecular devices as conductive modules and can be used to prepare supramolecular materials with switch performance.In addition,recent researches of CT compounds are introduced.In chapter 2,three coordination polymers(CPs):[MnL(bpp)]n(1)?[CdL(bpp)]n(2)and[Cd2L(bpp)2(H2O)(C2O4)0.5]n·n(Cl04)·.n(H2O)(3)were synthesized based on TTF-dicarboxylic and 1,3-bi(4-pyridyl)propane.Their structures are solved by single-crystal X-ray analysis.Compounds 1 and 2 are isostructural 2-D polymers,and 3 is an unusual 3-D MOF.We find a confinement effect of a 3-D MOF on the formation of charge-transfer TTF dimers.Additionally,photocurrent response were measured and the results proved MOFs with TTF dimers have relatively good photocurrent response.In chapter 3,two CT salts:Mebpe[Co(H2O)4]L2·2 H2O(4)and Mebpe[Ni(H2O)4]L2·2H20(5)were obtained through introducing transition metal ions and Mebpe cation into TTF system.Charge transfer properties of these compounds were studied through UV-vis spectra and cyclic voltammograms based on crystal structural analysis.The results showed that the TTF moieties are arranged in pairs in compounds 4 and 5.Strong charge-transfer occurs between cations and anions through weak C… C interactions.In addition,photocurrent response properties of these compounds were investigated and the results showed that compound 4 has a better photocurrent response.