TTF Derivatives Possessing Halogen-bond/long-alkyl Interactions: Synthesis And Supramolecular Assembly With The Spheric Molecules

Since the successful synthsis of the Tetrathiafulvalene?TTF?and the first organic conductor?TTF·TCNQ,TCNQ=7,7,8,8-Tetracyanoquinodimethane?,TTF and its derivatives have been widely appllied in the organic conductor,organic superconductor and organic magnetic materials.Comparing with the pristine TTF,arylthio-substituted/arylditithio-fused Tetrathiafulvalene derivatives have attracted our interest due to the two factors:on the one hand,the introduction of sulfur atoms into the TTF framework can effectively expand the size of?-system;on the other hand,the the peripheral aryl groups can easily adjust their arrangement to adapt to environmental variations.The role of the introducing the halogen atoms into the molecule can enhance the stability of the solid state structures and effect the electron distribution on the molecular skeleton.The molecules incorporating the long-alkyl chains not only have the fine solubility but also have the additional stability through the interdigitated long-alkyl chains.Considering these advantage,we decorated the peripheral phenyl groups of the phenylthio-substituted/benzodithio-fused TTF derivatives with the halogen atoms?F,Cl,and Br?/long-alkyl chains and focused on the efficiently synthesized method,properities and application on the assembly and so on.The study on the assembly includes the self-assembly and supramolecular assembly with the shape-and size-matched spheric molecules such as the fullerene and Keggin-type polyoxometallic acid.This thesis contains the following:Chapter 1:We briefly introduced the fellowing topics:firstly,halogen-bond interaction applied on the crystal engineering,soft materials and functional systems;secondly,the phenomenon of interdigitated long-alkyl chains and application of the long-alkyl chains in the liquid crystal materials;lastly,the modifiablity of TTF and application of the TTF derivatives.At the end of section,the basis and the contents were outline.Chapter 2:Nine fluorinated phenyl substituted/fused TTF derivatives via sulfur bridges including eight substituted and one fused TTF derivatives were designed and efficientlysynthesis.Theperfluorophenyl-substituted-and perfluorobenzo-fused-1,3-dithiole-2-thione derivatives are competing products in the same pot reaction.Through optimized the reaction conditions for the competing reactions,we found the best reaction conditions of the 1,3-dithiole-2-thione derivatives,respectively.Comparing the UV-Vis spectra of these TTF derivatives,the?_max of the perfluophenylthio-substituted TTF is significantly bathochromic shift than the phenylthio-substituted TTF.Additionally,we thoroughly analysized CV data and foundthattheE¹_1/2valuesofperfluorophenyl-substituted-and perfluorobenzo-fused-TTF derivatives are both maximum,para-fluorine atom is same as the hydrogen atom,ortho-fluorine atom increases the?E value,and meta-fluorine atom increases the E¹_1/2 value but decreases the?E value.Chapter 3:We reported the solid state structures of the title TTFs to elucidate the effects of the fluorine atoms on the crystallographic nature of TTFs.We have prepared the single crystals of 10 TTF derivatives and diffracted their cystal structures.Compound 9 had two different geometries and aggregations along the variable crystallization conditions.The F···S,C–F···?/?_F,C–F···F–C or C–H···F–C interaction was observed in these aggregations of TTF derivatives,and the number of the fluorine-contained interactions was more along the increasing of the number of fluorine atoms in the TTF derivatives.Specially,the C–F···F–C interactions played an vital role in the crystallization of the perfluorophenyl-substituted-TTF derivatives.Chapter 4:We reported supramolecular assembly of the halogenated phenylthio-substituted TTF derivatives with the Keggin-type polyoxometallic acid.We have prepared and recorded six single crystals of charge-transfer complexes between these TTF derivatives and the polyoxometalate anions.The ratios between TTF derivatives and polyoxometalate anions are 2:1.The cores of these TTF derivatives took the planar conformation and the TTF derivatives shown bown-type geometry when combined the peripheral aryl groups with the planar center in these complexes.The two TTF molecules and one polyoxometalate anion formed the sandwich-type building block.The building blocks packed into the 3-D structures through the several interactions.No matter the effect of the type and position of the halogen atoms,the the C–X···H–C?X=F,Cl or Br atom?and C–H···O interactions played an fundamental role in the aggregations.Excepting?1?₂·PMA·?H₂O?₄,the packing structures of these complexes shown the rectangular pores on the bc-plane and special peapod-type stacking structures on the ac-plane.It worthy noting that these complexes could recover into the netrual TTF derivatives when placed into the high hydrophilic solvents.We supposed the mechanism of recovery based on the experimental phenomena.Chapter 5:We prepared a series of encapsulated complexes between TTF derivatives?Donor?and fullerenes?Acceptor?including five halogenated TTF contained complexes and ten non-halogenated TTF contained complexes.According the differential ratio of the Donor/Acceptor,these complexes could devide into the type I?Donor/Acceptor=1/1?and type II?Donor/Acceptor=1/2?.The halogen atoms played a fundemental role in the aggregation of the complexes and easily formed the3-D frameworks that large enough to encapsulate the fullerene molecules.The composition of the co-crystals is thought to be the cooperative consequence of the molecular geometry of TTF derivatives,the shape and size of the fullerene molecule,the solvent adduct,and the crystallization dynamics.Moreover,by varing the peripheral aryls and solvents,the zero dimentional,one dimentional,two dimentional,and three dimentional packing motifs of fullerenes can be selecticely achieved.Chapter 6:We reported 12 multi-alkoxylated TTF derivatives.The3,4,5-trialkoxylated phenyl,2,3,4-trialkoxylated phenyl,and 2,4,6-trialkoxylated phenyl could effect the density of the electron on the core of TTF and fellow the order of 3,4,5-trialkoxylated phenyl<2,3,4-trialkoxylated phenyl<2,4,6-trialkoxylated phenyl.We found that the length of the alkyl chains had less effective to the E¹_1/2 and E²_1/2,but the TTF derivatives could show additional redox peaks and be liquid crystals along the larger of the alkyl chains.The more redox peaks were emerged due to the interdigitated of alkyl-chains formed the TTF dimers.In addition,we studied the UV-Vis spectra titration between the 3,4,5-trialkoxylated phenylthio-substituted TTF derivatives and C₆₀/Keggin-type polyoxometallic acid.