Polythiophenes have great potential as semiconductors for use in organic field effect transistors and light emitting diodes. Recent research has been focused on the design, synthesis and characterization of fluorinated polythiophenes and oligothiophenes. Various fluoroalkyl side chains have been introduced to induce polymer self-assembly, to control the electronic properties of the conjugated backbone, and to modify the solubility of the polymer in supercritical CO2. This work led to the preparation of poly(3-(perfluorooctyl)thiophene), which is one of only a few examples of n-dopable polythiophenes, and is the first supercritical CO2-soluble conducting polymer. An alternating copolymer consisting of 3-perfluoroakyl and 3-alkylthiophene units has been synthesized. This polymer, with alternating electron-donating and withdrawing substituents, has a high quantum yield for fluorescence in solution relative to the two homopolymers, and strong fluorescence in solid state. Based on the study on its nanocrystals, the unusual photophyiscs may be due to the formation of the supramolecular structure with hexagonal packing. A novel thiophene monomer, 3-(1,1-difluorooctyl)thiophene, was prepared to further tune the electronic structure of polythiophenes by changing the fluorination pattern of side chains, while retaining solubility in organic solvents by virtue of the hydrocarbon side chain. a-Hexyl-w-perfluorohexylsexithiophene was synthesized to make a novel amphiphilic material for use in TFTs. Models for interchain charge transfer in doped conducting polymers were also developed. Stacked and unstacked conjugated oligomers have been synthesized as models for conducting polymers. The bis(radical cation) form and the dication-neutral form of compounds in which conjugated oligomers are held in a stacked arrangement are shown to coexist and in equilibrium with each other. The coexistence of these two forms further suggests that both may serve as charge carriers. Interconversion between these forms by disproportionation mimics a possible mechanism for charge migration in doped conjugated polymers.

Philosophiae Doctor - PhD / This thesis is based on the study of electropolymerization and electrochromism of poly(4,7- dithien-2-yl-2,1,3-benzothiadiazole) (P(DTBT) and its copolymer with 3-methoxythiophene (MOT) in imidazolium ionic liquids (ILs) 1-butyl-3-methylimidazolium tetrafluoroborate (bmimbf4) hydrophilic, 1-butyl-3-methylimidazolium hexafluorophosphate (bmimpf6) and 1- butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (bmimtnf2) hydrophobic ILs. Traditional organic solvents acetonitrile and dichloromethane in the presence of 0.1 M tetrabutylammonium perchlorate (n-Bu4NClO4) as a supportive electrolyte was also used as a medium for comparison. Besides, a more hydrophobic ionic liquid, 1-octyl-3- methylimidazolium bis(trifluoromethylsulfonyl)imide (octmimtnf2) was also used for the electrodeposition of poly(3-methoxythiophene) (PMOT). The techniques employed are cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), uv-visible spectroelectrochemistry and scanning electron microscopy (SEM). 4,7-Dithien-2-yl-2,1,3-benzothiadiazole (DTBT) a type of donor –acceptor monomer and 3- methoxythiophene (MOT) has been electropolymerized using ionic liquids as growth and supportive electrolytes.