İki Farklı Elektron Verici-Alıcı-Verici Tip Elektrokrom İçeren Bir Elektrokromik Kopolimerin Sentezi ve Karakterizasyonu

İki farklı elektron verici-alıcı-verici tip monomer (EC ve TB) kullanılarak, elektroanalitik yöntemler ile elektrokromik bir kopolimer sentezlenmiştir. EC monomeri, elektron verici grup olarak 3,4-etilendiyoksitiyofen ve elektron alıcı grup olarak karbazole içerirken, TB monomeri elektron verici ve alıcı olarak sırasıyla tiyofen ve benzotiyadiyazol birimleri içermektedir. Elde edilen kopolimer, elektrokimyasal ve optiksel özellikleri bakımından incelenmiş ve bu özellikler EC ve TB homopolimerleri ile karşılaştırılmıştır. Kopolimer film, ilgili homopolimerlerden farklı özellikler göstermiştir. Nötral halde soluk turuncu olan EC polimeri ile morumsu renkteki TB polimeri, kopolimere dönüştüğünde iki polimerden gelen daha geniş bir bant aralığını kapatarak kahverengine dönüşmüştür. Homopolimerler ve kopolimerin fiziko-kimyasal özellikleri, enerji aralıkları, optik zıtlıkları ve renklenme verimleri sistematik olarak incelenmiştir.

Anahtar Kelimeler:

Electrochromic polymer, Electropolymerization, copolymerization

Synthesis and Characterization of an Electrochromic Copolymer Film Bearing Two Different Donor-Acceptor-Donor Type Electrochromes

Two donor-acceptor-donor type monomers (EC and TB) were selected to grow a copolymer via electrochemical techniques. EC monomer contains 3,4-ethylenedioxythiophene as the donor and carbazole as the acceptor units, while TB monomer includes thiophene and benzothiadiazole as the donor and the acceptor, respectively. The resulting copolymer film was investigated in terms of its electrochemical and optical properties and compared with the homopolymers of EC and TB. The copolymer film exhibited different electrochromic properties from their corresponding homopolymers. The neutral state faded-orange color of the polymer of EC and magenta color of the polymer of TB possesed a brownish color of the copolymer in the neutral state, with having a broader absorption band in the visible region by covering the characteristic absorption bands coming from both homopolymers. The physico-chemical properties, energy gaps, optical contrasts and coloring efficiencies for the homopolymers and for copolymer were systematically studied.

Keywords:

Electrochromic polymer, Electropolymerization, Copolymerization,

PDF

___

A. A. Argun, P. H. Aubert, B. C.Thompson, I. Schwendeman, C. L.Gaupp, J. Hwang, N. J. Pinto, D. B. Tanner, A. G. MacDiarmid, and J. R. Reynolds, “Multicolored electrochromism in polymers: structures and devices,” Chem Mater., 16, 4401-4412, 2004.
R. J. Mortimer, A. L. Dyer, and J. R. Reynolds, “Electrochromic organic and polymeric materials for display applications,” Display, 27, 2-18, 2006.
D. D. C. Bradley, “Conjugated polymer electroluminescence”, Synt. Met., 54, 401-415, 1993.
F. M. Kelly, L. L. Meunier, C. Cochrane, and V. Koncar, “Polyaniline: application as solid state electrochromic in a flexible textile display,” Displays, 34, 1-7, 2013.
A. Pennisi, F. Simone, G. Barletta, G. Di Marco, and L. Lanza, “Preliminary test of a large electrochromic window,” Electrochim. Acta, 44, 3237-3243, 1999.
R. Rauh, “Electrochromic windows: an overview”, Electrochim. Acta, 44, 3165-3176, 1999.
R. G. Mortimer, “Electrochromic materials,” Chem. Soc. Rev., 26, 147-156, 1997.
Z. E. X. Dance, M. J. Ahrens, A. M. Vega, A. B. Ricks, D. W. McCamant, M. A. Ratner, and M. R. Wasielewski, “Direct observation of the preference of hole transfer over electron transfer for radical ion pair recombination in donor-bridge-acceptor molecules,” J. Am. Chem. Soc., 130, 830-832, 2008.
G. Sonmez, H. B. Sonmez, C. K. F. Shen, R. W. Jost, Y. Rubin, and F. Wudl, “A processable green polymeric electrochromic,” Macromolecules, 38, 669-675, 2005.
H. Zhou, L. Yang, A. C. Stuart, S. C. Price, S. Liu, and W. You, “Development of fluorinated benzothiadiazole as a structural unit for a polymer solar cell of 7 % efficiency,” Angew. Chem., 123, 3051-3054, 2011.
S. Song, Y. Jin, S. H. Kim, J. Y. Shim, S. Son, I. Kim, K. Lee, and H. Suh, “Synthesis and characterization of polyfluorenevinylene with cyano group and carbazole unit,” J. Pol. Sci. Pol. Chem., 47, 6540-6551, 2009.
J. D. Froehlich, R. Young, T. Nakamura, Y. Ohmori, S. Li, and A. Mochizuk, “Synthesis of multi-functional POSS emitters for OLED applications,” Chem. Mater., 19, 4991-4997, 2007.
H. Usta, A. Facchetti, and T. J. Marks, “Air-stable, solution-processable n-channel and ambipolar semiconductors for thin-film transistors based on the indenofluorenebis(dicyanovinylene) core,” J. Am. Chem. Soc., 130, 8580-8581, 2008.
C. Yang, J. Y. Kim, S. Cho, J. K. Lee, A. J. Heeger, and F. Wudl, “Functionalized methanofullerenes used as n-type materials in bulk-heterojunction polymer solar cells and in field-effect transistors,” J. Am. Chem. Soc., 130, 6444-6450, 2008.
C. Malitesta, I. Losito, and P. G. Zambonin, “Molecularly imprinted electrosynthesized polymers: new materials for biomimetic sensors”, Anal. Chem., 71, 1366-1370, 1999.
R. John, M. Spencer, G. G. Wallace, and M. R. Smyth, “Development of a polypyrrole-based human serum albümin sensor,” Anal. Chim. Acta, 249, 381-385, 1991.
A. L. Dyer, E. J. Thompson, and J. R. Reynolds, “Completing the color palette with spray-processable polymer electrochromics,” Appl. Mater. Interf., 3, 1787-1795, 2011.
C. Duan, F. Huang, and Y. Cao, “Recent development of push-pull conjugated polymers for bulk-heterojunction photovoltaics: rational design and fine tailoring of molecular structures,” J. Mater. Chem., 22, 10416-10434, 2012.
H. Zhou, L. Yang, and W. You, “Rational design of high performance conjugated polymers for organic solar cells,” Macromolecules, 45, 607-632, 2012.
A. Durmus, G. Gunbas, P. Camurlu, and L. Toppare, “Neutral state green polymer with a superior transmissive light blue oxidized state,” Chem. Commun., 31, 3246-3248, 2007.
A. Durmus, G. Gunbas, and L. Toppare, “New, highly stable electrochromic polymers from 3,4-ethylenedioxythiophene-bis-substituted quinoxalines toward greeen polymeric materials,” Chem. Mater., 19, 6247-6251, 2007.
J. Mei, and Z. Bao, “Side chain engineering in solution processable conjugated polymers,” Chem. Mater., 26, 604-615, 2014.
R. S. Kularatne, H. D. Magurudeniya, P. Sista, M. C. Biewer, and M. C. Stefan, “Donor-acceptor semiconducting polymers for organic solar cells,” J. Pol. Sci. Part A: Pol. Chem., 51, 743-768, 2013.
T. Hardeman, and G. Koeckelberghs, “Synthesis of conjugated polymers by combining different coupling reactions,” Pol. Chem., 27, 3999-4004, 2017.
R. Xie, Z. Chen, G. Zhang, Y. Huang, L. Ying, F. Huang, and Y. Cao, “Synthesis and characterization of p-conjugated copolymers based on alkyltriazolyl substituted benzodithiophene,” New J. Chem., 40, 4727-4734, 2016.
H. Sun, B. Lu, X. Duan, J. Xu, L. Dong, X. Zhu, K. Zhang, D. Hu, and S. Ming, “Electrosynthesis and characterization of a new conducting copolymer from 2’-aminomethyl-3,4-ethylenedioxythiophene and 3,4-ethylenedioxythiophene,” Int. J. Electrochem. Sci., 10, 3236-3249, 2015.
G. Nie, L. Qu, J. Xu, and S. Zhang, “Electrosyntheses and characterizations of a new soluble conducting copolymer of 5-cyanoindole and 3,4-ethylenedioxythiophene,” Electrochim. Acta, 53, 8351-8358, 2008.
A. Aydın, and I. Kaya, “Syntheses and characterization of yellow and green light emitting novel polymers containing carbazole and electroactive moieties,” Electrochim. Acta, 65, 104-114, 2012.
A. Aydın, and I. Kaya, “Syntheses of novel copolymers containing carbazole and their electrochromic properties,” J. Electroanal. Chem., 691, 1-12, 2013.
M. Ates, and N. Uludag, “Carbazole derivative synthesis and their electropolymerization,” J. Solid State Electrochem., 20, 587-597, 2016.
B. B. Carbas, “Novel electrochromic copolymers based on 3-3’-dibromo-2-2’bithiophene and 3,4-ethylenedioxythiophene,” Polymer, 113, 180-186, 2017.
M. Akbayrak, E. G. Cansu-Ergun, and A. M. Onal, “Synthesis and electro-optical properties of a new copolymer based on EDOT and carbazole,” Des. Monomers Pol., 19, 679-687, 2016.
E. G. Cansu-Ergun, “Covering the more visible region by electrochemical copolymerization of carbazole and benzothiadiazole based donor-acceptor type monomers,” Chin. J. Polym. Sci., 37, 28-35, 2019.
E. G. Cansu-Ergun, and A. M. Onal, “Carbazole based electrochromic polymers bearing ethylenedioxy and propylenedioxy scaffolds,” J. Electroanal. Chem., 815, 158-165, 2018.
E. G. Cansu-Ergun, M. Akbayrak, A. Akdag, and A. M. Onal, “Effect of thiophene units on the properties of donor-acceptor type monomers and polymers bearing thiophene-benzothiadiazole-scaffolds,” J. Electrochem. Soc., 163, 1-6, 2016.
H. P. Zhao, X. T. Tao, F. Z. Wang, Y. Ren, X. Q. Sun, J. X. Yang, Y. X. Yan, D. C. Zou, X. Zhao, and M. H. Jiang, “Transport materials for organic light-emitting diodes,” Chem. Phys. Lett., 439, 132–137, 2007.
J. L. Bredas, and G. B. Street, “Polarons, bipolarons and solitons in conducting polymers,” Acc. Chem. Res., 18, 309-315, 1985.
J. Bakalis, A. R. Cook, S. Asaoka, M. Forster, U. Scherf, J. R. Miller, “Polaronsi compressed polarons and bipolarons in conjugated polymers,” J. Phys. Chem. C., vol. 118, pp. 114-125, 2014.
P. M. Beaujuge, and J. R. Reynolds, “Color control in p-conjugated organic polymers for use in electrochromic devices,” Chem Rev., 110, 268-320, 2010.