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    Effect of the planar center moiety for a donor-acceptor polymeric electrochrome
    (Elsevier Sci Ltd, 2017) Doyranli, Ceylan; Colak, Betul; Lacinel, Gozde; Can, Mustafa; Koyuncu, Fatma Baycan; Koyuncu, Sermet
    In this work, phenanthrene centered donor-acceptor monomer; 5,10-bis(4-hexyl-2-thienyl)phenantro [9,10-c][1,2,5]thiodiazole; MES16 was synthesized and then its electrochromic application of corresponding polymer was carried out. 4,7-di(thiophen-2-yl)-2,1,3-benzothiadiazole (TST) was also synthesized as a standard molecule to determine the effect of the planar phenanthrene center on electrochromic performance. Electrochemical properties were elucidated by cyclic voltammetry and then HOMO-LUMO band gaps were calculated by using their oxidation and reduction onset potentials. Finally, electrochromic properties of poly-(MES16) and poly-(TST) were investigated via spectro-electrochemical measurements. DFT calculations exhibit that poly-(MES16) has a high planarity and an intramolecular charge transfer from the polymer backbone-donor to thiadiazole-acceptor subunit. Because of high solid state it it interactions of the poly-(MES16), a good quality film was obtained corresponding to self assembly property planar phenantrene center. Owing to this property, electrochromic performance of poly-(MES16) such as response time, stability and Delta T% were better than the standard poly-(TST). (C) 2016 Elsevier Ltd. All rights reserved.
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    Electrochromic properties of phenantrene centered EDOT polymers
    (Elsevier Sci Ltd, 2017) Colak, Betul; Buyukkoyuncu, Ahmet; Koyuncu, Fatma Baycan; Koyuncu, Sermet
    A series of phenantrene centered donor-acceptor type electroactive 3,4-ethlenedioxythiophene (EDOT) monomers (EP-X) containing N, S and Se heteroatom on the bezophenantra-X-diazole acceptor unit have been synthesized by Stille coupling reaction. These monomers were electrochemically polymerized by potentiodynamic method to obtain electrochromic polymer films. Spectro-electrochemical properties were also investigated by UV-vis absorption connected with the cyclic voltammetry measurements. The polymer films exhibited a remarkable trend of visible color (yellow, orange, red) at the neutral state due to changing the central acceptor moiety. These polymer films have multielectrochromic properties by means of moderately changing the absorbance/transmittance at the visible regime upon applied positive potentials. The donor-acceptor interaction at the neutral state correlated by DFT calculations was also supported by the interesting trend in the colors of these polymers. Finally, the electrochromic performance of EP-X polymer films represented a high redox stability, reasonable contrast ratio, coloration efficiency and response times. (C) 2017 Elsevier Ltd. All rights reserved.
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    Tuning the Electrochromic Properties of Fluorinated Benzochalcogenodiazole Based Donor-Acceptor Polymers
    (Wiley-V C H Verlag Gmbh, 2020) Colak, Betul; Altinisik, Sinem; Koyuncu, Fatma Baycan; Canimkurbey, Betul; Koyuncu, Sermet
    In this study, a series of benzochalcogenodiazole based donor acceptor monomers namely 4,7-bis(4-hexyl-2-thienyl)-2,1,3-benzothiadiazole (TST), 5,6-difluoro-4,7-bis(4-hexyl-2-thienyl)-2,1,3-benzothiadiazole (TST2) and 4,7-bis(4-hexyl-2-thienyl)-2,1,3-benzoselenadiazole (TSeT) were synthesized by Stille reaction and then directly polymerized on to Indium Tin Oxide coated glass (ITO/Glass) surface by electrochemical polymerization process. According to UV-Vis measurements, a 20 nm blue shift was detected at low energy band after fluorination of TST (TST2). Besides, a 40 nm red shift was observed by changing S to Se on the benzochalcogenodiazole moiety (TSeT). Thus, the optical band gaps were varied as 2.32, 2.45 and 2.16 eV for TST, TST2 and TSeT, respectively. According to AFM results, rougher surface was observed in the PTSeT thin film than that of PTST and PTST2. Thin films of electrodeposited polymers onto ITO/glass surface displayed ambipolar multi-electrochromic behavior both anodic and cathodic region. The ambipolar charge distribution was also observed in the theoretical DFT calculations. When the electrochromic performance of the polymer films was compared to each other, it was seen that the PTST2 has a better stability and higher the percentage transmittance change (Delta T%) at near-IR regime between neutral and oxidized states.