Controlled Assembly Of Arylthio-substituted Tetrathiafulvalene Derivatives And Photoelectric Properties Of Assembly Materials

The organic functional materials always a hot research topic and they can be applied to energy,information storage and transmission,optical communication,stealth and bionic applications presented attractive prospects.The donor-acceptor type（D–A）organic materials have aroused researchers’attention due to the various of D–A system and their electro-optical properties and conductivities can be influenced by the inner interactions.Meantime,they can be a better successor to electronic devices and renewable energy.Since the successful synthesis of tetrathiafulene（TTF）and the first organic conductor TTF·TCNQ were reported,TTF and its derivatives are widely used to organic conductor and magnetic organic conductor for good electron supplying ability.Our group has disclosed a facile and efficient synthesis method of the flexible arylthiol-substituted tetrathiafulvalene derivatives（Ar-S-TTFs）.On the one hand,Ar-S-TTFs are electron-donor moleculars.On the other hand,it is found that the peripheralaryls on Ar-S-TTFs show rotational freedom around two C-S bonds,and change their configuration with the surrounding environment.Therefore,Ar-S-TTFs have their own advantages in charge transfer complexs.Considering these advantages,we studied the synthesis,structure and partial physical properties of charge transfer salts of the Ar-S-TTFs with transition metals,TCNQF₄ and iodine.Besides,in order to enhance the ability of the electron donor of the Ar-S-TTF,we synthesized the flexible exTTF derivatives and studied photoelectric properties and molecular assembly.Chapter 1:We briefly introduced the following topics:firstly,the research background of TTF and its derivatives;secondly,the development of TTF derivatives;finally,the basis and the contents were outline.Chapter 2:We reported molecular assembly of flexible Ar-S-TTFs with CuBr₂/FeBr₃.According to the differential valence of Ar-S-TTFs,the compounds could devide into the typeⅠ（the charge on TTF derivatives is+1）and the typeⅡ（the charge on TTF derivatives is+2）.In the crystal structures of these charge-transfer salts,the counter anions can be distorted linear-type[CuBr₂]^-,tetrahedron-type[CuBr₄]^-,octahedral configuration-type[Cu₂Br₆]^2-and tetrahedron-type[FeBr₄]^-.The stacking structures show the introduction of the halogen atoms into the TTFs can increase the intermolecular interactions.Chapter 3:Sixteen types molecular assembly material of flexible Ar-S-TTFs with I₂ were reported.The structures of polyiodides in CT complexes can be manipulated by varying the symmetry and size of aryls on Ar-S-TTFs,and a variety of polyiodides are formed to be 1-D chain,and 2-D/3-D networks composed of（I₃）^–and I₂,The degree of charge transfer was different in liquid and charge-transfer salt and the charge of Ar-S-TTFs in the composite is inconsistent with their redox potential.This may be related to the redox potential of Ar-S-TTFs and iodine and the crystal structures.Chapter 4:Seven types of organic-organic molecular assembly materials of Ar-S-TTFs with TCNQF₄ were obtained by two different crystal growth methods.Charge transfer is the primary condition for the formation of charge-transfer salts crystals.We get the charge of TTF derivatives in the charge-transfer salts throunth two different ways and the results are consistent.The crystals present two different packings:separate column and mixed column.The conductance tests show that the separate columns of charge-transfer salts crystals have moderate conductivity.They are semiconductor.Chapter 5:We found the structural phase transition of the molecular assembly material of TTF-p-CH₃ and TCNQF₄ when the temperature changed.Four structural phase transitions happen in the region of 300 k-50 k through conductance testing,DSC,magnetic and XRD.We found the cause of structural phase transition is the change of electron-phonon coupling due to the diffdrent of temperature,which leads to the constant change of charge distribution and intermolecular.Chapter 6:Four arylthio-substituted flexible exTTF derivatives were designed and efficiently synthesis.We found they are good donors by analyzing electron characteristics.We reported five different charge-transfer salts of exTTF derivatives and studied their crystal structures finding the different configuration of exTTF derivatives on the oxidation state with neutral.The different aryls on exTTF derivatives have a great influence on the structure and intermolecular interaction of the C-T salts.