Organic semi-conductors are of great interest since these compounds can be utilized as active layers in many device applications such as ECDs, LEDs and solar cells. Incorporating the benzotriazole units into the polymer backbone enhances the optical properties of donor units. Hexyl thiophene and pyrrole are commonly used as electron donor materials. Benzotriazole can be coupled to hexyl thiophene or pyrrole to yield materials which can be polymerized to give donor acceptor type polymers. These materials are promising components in fast switching polymeric electrochromic devices and highly efficient photovoltaic devices. During thesis studies,poly(2-dodecyl-4,7-bis(4-hexylthiophen-2-yl)-2H-benzo[d][1,2,3]triazole) (PHTBT) and poly(2-dodecyl-4,7-di(1H-pyrrol-2-yl)- 2H- benzo [d] [1,2,3] triazole) (PPyBT) will be synthesized via N-alkylation, bromination, stannylation and Stille coupling reactions. Electrochromic and photovoltaic properties of the polymers will be investigated in detail.

A proven strategy, donor-acceptor approach, to reduce the band gap of conjugated materials and possibly improve the photocurrent is to incorporate electron-rich and electron-deficient units in an alternating fashion in a polymer chain. For this purpose, a wise selection of donor and acceptor moieties in a monomer structure results in desired finishing properties of polymeric materials. In this study, fourteen novel monomers were synthesized to explore the acceptor and donor effects on the electronic and optoelectronic properties. Dibenzophenazine, dibenzopyrido]quinoxaline, tetrahydro- dibenzophenazine, thiadiazoloquinoxaline, pyrazinoquinoxaline, thienopyrazine, benzoselenadiazole, thienoselenadiazole were used as acceptor moieties, while thiophene, 3-hexylthiophene and 2,3-dihydrothienodioxine (EDOT) were used as the donor components in these donor-acceptor molecules. To synthesize desired monomers, well-known synthetic methods were performed, including bromination, nitration, reduction and condensation. Bromination was achieved by two different ways depends on the aim, NBS and Br2/HBr medium. For the nitration, HNO2 and H2SO4 were used together. Fe metal in refluxing acetic acid was used as the reducing agent in case of nitro group reductions. On the other hand, Zn metal/AcOH system was chosen for the reduction of both nitro groups and thiadiazole structure to amine, simultaneously. Finally, the Stille Coupling was used to obtain resulting acceptor-donor-acceptor monomers. These synthesized monomers were polymerized by electrochemically and investigated their properties by methods such as spectroelectrochemistry, kinetic and colorimetry studies. Spectroelectrochemistry experiments were performed in order to investigate key properties of conducting polymers such as band gap, maximum absorption wavelength, the intergap states that upon doping and evolution of polaron and bipolaron bands. Switching time and optical contrast of the polymers were evaluated via kinetic studies.

5,8-Bis(2,3-dihydrothieno[3,4b][1,4]dioxin-5-yl)-2-(naphthalen-2-yl)-3-ferrocenyl-4a,8a-dihydroquinoxaline (DEFNQ), 5,8-bis(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-2-(phenyl)-3 ferrocenylquinoxaline (DEFPQ) and 5,8-bis(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-2,3-di(naphthalen-2-yl)quinoxaline (DEDNQ) were synthesized, electrochemically polymerized and electrochromic properties of resultant polymers were investigated. For the characterization of the monomers Nuclear Magnetic Resonance (1H-NMR, 13C-NMR) were used. Cyclic Voltammetry (CV) and Ultraviolet&ndash / Visible Spectroscopy were used to investigate electrochemical behavior of the monomers and redox reactions of conducting polymers. After electrochemical polymerizations, the electrochromic properties of the conducting polymers were investigated via spectroelectrochemistry, kinetic and colorimetry studies to explore the one of most important property of conducting polymers, the ability to switch reversibly between the two states of different optical properties, &lsquo / electrochromism&rsquo / . Cyclic Voltammetry and Spectroelectrochemistry studies for PDEFNQ, PDEFPQ and PDEDNQ showed that ferrocenyl (Fc) group containing derivatives are multichromic green to transmissive polymer with high tendency to be both p and n doped. PDEDNQ which was not functionalized with ferrocenyl group does not show multichromism. According to the electrochemical and spectroscopic results each polymer is a potential candidate for optoelectronic applications.

ABSTRACT SYNTHESIS OF BENZIMIDAZOLE CONTAINING DONOR ACCEPTOR ELECTROCHROMIC POLYMERS Akpinar, Hava Zekiye M. Sc., Department of Chemistry Supervisor: Prof. Dr. Levent Toppare February 2011, 60 pages Donor-acceptor-donor (DAD) type benzimidazole (BIm) and 3,4-ethylenedioxythiophene (EDOT) bearing monomers (4-(2,3-Dihydrothieno[3,4-b][1,4]dioxin-5-yl)-7-(2,3 dihydrothieno[3,4b][1,4] dioxin-7-yl)-2-benzyl-1H-benzo[d]imidazole (M1), 2,4-bis(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-7-(2,3-dihydrothieno[3,4-b][1,4]dioxin-7-yl)-1H-benzo[d]imidazole (M2) and 4-(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-7-(2,3-dihydrothieno[3,4-b][1,4]dioxin-7-yl)-2-ferrocenyl-1H-benzo[d]imidazole (M3)) were synthesized and electrochemically polymerized. Pendant group at 2-C position of the imidazole ring was functionalized with phenyl (P1), EDOT (P2) and ferrocene (P3) in order to observe substituent effect on electrochemical and electrochromic properties of corresponding polymers. Spectroelectrochemical results showed that different pendant groups resulted in polymers with slightly different optical band gaps (1.75, 1.69 and 1.77 eV respectively) and different number of achievable colored states. Optoelectronic performance were reported in detail. Keywords: Benzimidazole, EDOT, Donor-Acceptor Type Polymers, Electrochromism, Conjugated Polymers.

ABSTRACT SYNTHESIS OF BENZIMIDAZOLE CONTAINING DONOR ACCEPTOR ELECTROCHROMIC POLYMERS Akpinar, Hava Zekiye M. Sc., Department of Chemistry Supervisor: Prof. Dr. Levent Toppare February 2011, 60 pages Donor-acceptor-donor (DAD) type benzimidazole (BIm) and 3,4-ethylenedioxythiophene (EDOT) bearing monomers (4-(2,3-Dihydrothieno[3,4-b][1,4]dioxin-5-yl)-7-(2,3 dihydrothieno[3,4b][1,4] dioxin-7-yl)-2-benzyl-1H-benzo[d]imidazole (M1), 2,4-bis(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-7-(2,3-dihydrothieno[3,4-b][1,4]dioxin-7-yl)-1H-benzo[d]imidazole (M2) and 4-(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-7-(2,3-dihydrothieno[3,4-b][1,4]dioxin-7-yl)-2-ferrocenyl-1H-benzo[d]imidazole (M3)) were synthesized and electrochemically polymerized. Pendant group at 2-C position of the imidazole ring was functionalized with phenyl (P1), EDOT (P2) and ferrocene (P3) in order to observe substituent effect on electrochemical and electrochromic properties of corresponding polymers. Spectroelectrochemical results showed that different pendant groups resulted in polymers with slightly different optical band gaps (1.75, 1.69 and 1.77 eV respectively) and different number of achievable colored states. Optoelectronic performance were reported in detail.

2-Dodecyl benzotriazole (BTz) and benzothiadiazole (BTd) containing copolymers poly(4-(2-dodecyl-2H-benzo[d][1,2,3]triazol-4-yl)benzo[c][1,2,5]thiadiazole (P1), poly(4-(5-(2-dodecyl-7-(thiophen-2yl)-2H-benzo[d][1,2,3]triazol-4-yl)thiophen-2-yl)benzo[c][1,2,5] thiadiazole (P2) and poly(4-(5-(2-dodecyl-7-(4-hexylthiophen-2-yl)-2H-benzo[d] [1,2,3]triazol-4-yl) -3-hexylthiophen-2-yl) benzo[c][1,2,5] thiadiazole (P3) were synthesized via Suzuki polymerization. Electrochemical and optical properties of the polymers were analyzed. The fabrication of solar cells were carried out and current density-voltage (J-V) and incident photon to charge carrier efficiency (IPCE) measurements were done to characterize the solar cells.

The interest towards organic semi-conductors increased due to their tunable band gaps, redox properties, processability and low cost in the field of conducting polymers. Electrochromic materials have the ability to change color by altering their redox state. In the context of low cost flexible display device technology, requirements can be fulfilled with accessible multi-colored electrochromic polymers. In this study, we report the chemical synthesis and electrochromic properties of two spray processable, ambipolar, fluorescent and multi-color to transmissive electrochromic polymers. The electrochromic properties of these polymers were examined by cyclic voltammetry, spectroelectrochemistry, kinetic studies. Polymers, PTBTPh and PTBTTh, have multi-colored oxidation states and easily accessible ndoped states, which allowed us to achieve transmissive films in a low working potential. Electrochemical and spectral results showed that both polymers are potential materials for electrochromic display devices.

In this study, a novel series of conjugated monomers containing furan and fluorene units / 2,7-di(furan-2-yl)-9H-fluoren-9-one (FOF), 2-(2-(furan-2-yl)-9H-fluoren-7-yl)furan (FFF), and 2-(2-(furan-2-yl)-9,9-dihexyl-9H-fluoren-7-yl)furan (FHF) were synthesized and their electrochemical polymerization were achieved via potential cycling. Optical and electrochemical properties of the polymers, poly(2,7-di(furan-2-yl)-9H-fluoren-9-one) (PFOF), poly(2-(2-(furan-2-yl)-9H-fluoren-7-yl)furan (PFFF) and poly(2-(2-(furan-2-yl)-9,9-dihexyl-9H-fluoren-7-yl)furan) (PFHF) were investigated and it was found that polymer films exhibit reversible redox behavior (Epox = 1.083 V for PFOF, Epox= 0.915 V for PFFF and Epox= 0.985 V for PFHF) accompanied with a reversible electrochromic behavior, orange to green for PFOF, yellow to dark blue for PFFF and orange to green for PFHF during oxidation. Their band gap values (Eg) were found to be 2.32, 2.49 and 2.61 eV for PFOF, PFFF and PFHF, respectively.

Donor-acceptor-donor approach is one of the effective ways to synthesize low band gap polymers. The monomers that will be designed with respect to donor-acceptor-donor approach have low band gap achieved by the coupling of a strong donor with high HOMO level to a strong acceptor with low LUMO level. Thus, the new donor-acceptor material will have a reduced bandgap (Eg) relative to either of its parent components. Due to this point of view, in this study, new electroactive benzothiadiazole and 2,3-bis(4-(tert-butyl)phenyl)quinoxaline monomers substituted with different donor groups (3,4-ethylenedioxythiophene and thiophene) were synthesized to explain the effect of different donor groups on the electronic and optical properties of DAD type polymers. The characterizations of the monomers were performed by 1H and 13C NMR techniques. Electrochemical behavior of both monomers and polymers were studied by cyclic voltammetry. The electrochromic properties of the synthesized conducting polymers were investigated by several methods like spectroelectrochemistry, kinetic and colorimetry studies. The polymers have two different donor units may behave as a copolymer of the symmetric monomer having the same donor groups. Hence, the properties of copolymers were investigated with the co-monomers having either thiophene or 3,4-ethylenedioxythiophene as the donor group.

Thesis (Ph. D.)--University of Missouri-Columbia, 2001. / Typescript. Vita. Includes bibliographical references. Also available on the Internet.