We report the facile and economical synthesis of an electrochromic copolymer for black based on electrochemical copolymerization of thiophene and 3, 4-ethylenedioxythiophene in boron trifluoride diethyl etherate. The resultant copolymer presents multicolor electrochromism with reversible color change between drab color and blue black. Furthermore, in the polar state the resultant copolymer shows strong and broad absorption in the whole visible region and then exhibits black color. The copolymer presents a transmittance variation of 25% at 522 nm, and corresponding response times for bleaching and coloration are 4.2 and 3.3 s, respectively. Good electrochemical stability can be achieved by the copolymer film, which retains 87% of its original electroactivity after 2000 cycles.

© 2012 OSA

1. C. Ma, M. Taya, and C. Xu, “Flexible electrochromic device based on poly(3,4-(2,2 dimethylpropylenedioxy)thiophene),” Electrochim. Acta54(2), 598–605 (2008). [CrossRef]
2. S. V. Vasilyeva, P. M. Beaujuge, S. Wang, J. E. Babiarz, V. W. Ballarotto, and J. R. Reynolds, “Material strategies for black-to-transmissive window-type polymer electrochromic devices,” ACS. Appl. Mater. Inter.3(4), 1022–1032 (2011). [CrossRef]
3. P. R. Somani and S. Radhakrishnan, “Electrochromic materials and devices: present and future,” Mater. Chem. Phys.77(1), 117–133 (2003). [CrossRef]
4. D. Baran, G. Oktem, S. Celebi, and L. Toppare, “Neutral-state green conjugated polymers from pyrrole bis-substituted benzothiadiazole and benzoselenadiazole for electrochromic devices,” Macromol. Chem. Phys.212(8), 799–805 (2011). [CrossRef]
5. P. M. Beaujuge and J. R. Reynolds, “Color control in π-conjugated organic polymers for use in electrochromic devices,” Chem. Rev.110(1), 268–320 (2010). [CrossRef] [PubMed]
6. A. C. Kucuk, F. Yilmaz, H. Can, H. Durmaz, A. Kosemen, and A. E. Muftuoglu, “Synthesis of a novel macroinimer based on thiophene and poly(e-caprolactone) and its use in electrochromic device application,” J. Polymer. Sci. Pol. Chem.49, 4180–4192 (2011).
7. H. Yoon, M. Chang, and J. Jang, “Formation of 1D poly(3,4-ethylenedioxythiophene) nanomaterials in reverse microemulsions and their application to chemical sensors,” Adv. Funct. Mater.17(3), 431–436 (2007). [CrossRef]
8. S. Beaupre, A. C. Breton, J. Dumas, and M. Leclerc, “Multicolored electrochromic cells based on poly(2,7-carbazole) derivatives for adaptive camouflage,” Chem. Mater.21(8), 1504–1513 (2009). [CrossRef]
9. P. M. Beaujuge, S. Ellinger, and J. R. Reynolds, “The donor-acceptor approach allows a black-to-transmissive switching polymeric electrochrome,” Nat. Mater.7(10), 795–799 (2008). [CrossRef] [PubMed]
10. P. Shi, C. M. Amb, E. P. Knott, E. J. Thompson, D. Y. Liu, J. Mei, A. L. Dyer, and J. R. Reynolds, “Broadly absorbing black to transmissive switching electrochromic polymers,” Adv. Mater. (Deerfield Beach Fla.)22(44), 4949–4953 (2010). [CrossRef] [PubMed]
11. M. Içli, M. Pamuk, F. Algı, A. M. Önal, and A. Cihaner, “A new soluble neutral state black electrochromic copolymer via a donor–acceptor approach,” Org. Electron.11(7), 1255–1260 (2010). [CrossRef]
12. X. H. Xia, J. P. Tu, J. Zhang, X. H. Huang, X. L. Wang, W. K. Zhang, and H. Huang, “Multicolor and fast electrochromism of nanoporous NiO/poly(3,4-ethylenedioxythiophene) composite thin film,” Electrochem. Commun.11(3), 702–705 (2009). [CrossRef]
13. P. Camurlu, Z. Bicil, C. Gültekin, and N. Karagoren, “Novel ferrocene derivatized poly(2,5-dithienylpyrrole)s: Optoelectronic properties, electrochemical copolymerization,” Electrochim. Acta63, 245–250 (2012). [CrossRef]
14. B. Sankaran and J. R. Reynolds, “High-contrast electrochromic polymers from alkyl-derivatized poly(3,4-ethylenedioxythiophenes),” Macromolecules30(9), 2582–2588 (1997). [CrossRef]
15. P. Camurlu, S. Tarkuc, E. Sahmetlioglu, I. M. Akhmedov, C. Tanyeli, and L. Toppare, “Multichromic conducting copolymer of 1-benzyl-2,5-di(thiophen-2-yl)- 1H-pyrrole with EDOT,” Sol. Energy Mater. Sol. Cells92(2), 154–159 (2008). [CrossRef]
16. S. Akoudad and J. Roncali, “Modification of the electrochemical and electronic properties of electrogenerated poly(3,4-ethylenedioxythiophene) by hydroxymethyl and oligo(oxyethylene) substituents,” Electrochem. Commun.2(1), 72–76 (2000). [CrossRef]
17. A. Kumar, D. M. Welsh, M. C. Morvant, F. Piroux, K. A. Abboud, and J. R. Reynolds, “Conducting poly(3,4-alkylenedioxythiophene) derivatives as fast electrochromics with high-contrast ratios,” Chem. Mater.10(3), 896–902 (1998). [CrossRef]
18. R. J. Mortimer, A. L. Dyer, and J. R. Reynolds, “Electrochromic organic and polymeric materials for display applications,” Displays27(1), 2–18 (2006). [CrossRef]
19. J. Heinze, B. A. Frontana-Uribe, and S. Ludwigs, “Electrochemistry of conducting polymers persistent models and new concepts,” Chem. Rev.110(8), 4724–4771 (2010). [CrossRef] [PubMed]
20. G. Shi, S. Jin, G. Xue, and C. Li, “A conducting polymer film stronger than aluminum,” Science267(5200), 994–996 (1995). [CrossRef] [PubMed]
21. S. Shi, C. Li, and Y. Liang, “High-strength conducting polymers prepared by electrochemical polymerization in boron trifluoride diethyl etherate solution,” Adv. Mater. (Deerfield Beach Fla.)11(13), 1145–1146 (1999). [CrossRef]
22. S. Alkan, C. A. Cutler, and J. R. Reynolds, “High quality electrochromic polythiophenes via BF3.Et2O electropolymerization,” Adv. Funct. Mater.13(4), 331–336 (2003). [CrossRef]
23. K. Krishnamoorthy, M. Kanungo, A. Q. Contractor, and A. Kumar, “Electrochromic polymer based on a rigid cyanobiphenyl substituted 3,4-ethylenedioxythiophene,” Synth. Met.124(2-3), 471–475 (2001). [CrossRef]
24. C. Zhang, Y. Xu, N. Wang, Y. Xu, W. Xiang, M. Ouyang, and C. Ma, “Electrosyntheses and characterizations of novel electrochromic copolymers based on pyrene and 3,4-ethylenedioxythiophene,” Electrochim. Acta55(1), 13–19 (2009). [CrossRef]
25. C. Zhang, C. Hua, G. Wang, O. Mi, and C. Ma, “A novel multichromic copolymer of 1,4-bis(3-hexylthiophen-2-yl)benzene and 3,4-ethylenedioxythiophene prepared via electrocopolymerization,” J. Electroanal. Chem.64, 54–61 (2010).
26. A. Patra, Y. H. Wijsboom, S. S. Zade, M. Li, Y. Sheynin, G. Leitus, and M. Bendikov, “Poly(3,4-ethylenedioxyselenophene),” J. Am. Chem. Soc.130(21), 6734–6736 (2008). [CrossRef] [PubMed]
27. G. E. Gunbas, P. Camurlu, I. M. Akhmedov, C. Tanyeli, A. M. Onal, and L. Toppare, “A fast switching, low band gap, p- and n-dopable, donor–acceptor type polymer,” J. Electroanal. Chem.615(1), 75–83 (2008). [CrossRef]

ACS. Appl. Mater. Inter.

• S. V. Vasilyeva, P. M. Beaujuge, S. Wang, J. E. Babiarz, V. W. Ballarotto, and J. R. Reynolds, “Material strategies for black-to-transmissive window-type polymer electrochromic devices,” ACS. Appl. Mater. Inter.3(4), 1022–1032 (2011). [CrossRef]

Adv. Funct. Mater.

• H. Yoon, M. Chang, and J. Jang, “Formation of 1D poly(3,4-ethylenedioxythiophene) nanomaterials in reverse microemulsions and their application to chemical sensors,” Adv. Funct. Mater.17(3), 431–436 (2007). [CrossRef]
• S. Alkan, C. A. Cutler, and J. R. Reynolds, “High quality electrochromic polythiophenes via BF3.Et2O electropolymerization,” Adv. Funct. Mater.13(4), 331–336 (2003). [CrossRef]

Adv. Mater. (Deerfield Beach Fla.)

• S. Shi, C. Li, and Y. Liang, “High-strength conducting polymers prepared by electrochemical polymerization in boron trifluoride diethyl etherate solution,” Adv. Mater. (Deerfield Beach Fla.)11(13), 1145–1146 (1999). [CrossRef]
• P. Shi, C. M. Amb, E. P. Knott, E. J. Thompson, D. Y. Liu, J. Mei, A. L. Dyer, and J. R. Reynolds, “Broadly absorbing black to transmissive switching electrochromic polymers,” Adv. Mater. (Deerfield Beach Fla.)22(44), 4949–4953 (2010). [CrossRef] [PubMed]

Chem. Mater.

• A. Kumar, D. M. Welsh, M. C. Morvant, F. Piroux, K. A. Abboud, and J. R. Reynolds, “Conducting poly(3,4-alkylenedioxythiophene) derivatives as fast electrochromics with high-contrast ratios,” Chem. Mater.10(3), 896–902 (1998). [CrossRef]
• S. Beaupre, A. C. Breton, J. Dumas, and M. Leclerc, “Multicolored electrochromic cells based on poly(2,7-carbazole) derivatives for adaptive camouflage,” Chem. Mater.21(8), 1504–1513 (2009). [CrossRef]

Chem. Rev.

• P. M. Beaujuge and J. R. Reynolds, “Color control in π-conjugated organic polymers for use in electrochromic devices,” Chem. Rev.110(1), 268–320 (2010). [CrossRef] [PubMed]
• J. Heinze, B. A. Frontana-Uribe, and S. Ludwigs, “Electrochemistry of conducting polymers persistent models and new concepts,” Chem. Rev.110(8), 4724–4771 (2010). [CrossRef] [PubMed]

Displays

• R. J. Mortimer, A. L. Dyer, and J. R. Reynolds, “Electrochromic organic and polymeric materials for display applications,” Displays27(1), 2–18 (2006). [CrossRef]

Electrochem. Commun.

• X. H. Xia, J. P. Tu, J. Zhang, X. H. Huang, X. L. Wang, W. K. Zhang, and H. Huang, “Multicolor and fast electrochromism of nanoporous NiO/poly(3,4-ethylenedioxythiophene) composite thin film,” Electrochem. Commun.11(3), 702–705 (2009). [CrossRef]
• S. Akoudad and J. Roncali, “Modification of the electrochemical and electronic properties of electrogenerated poly(3,4-ethylenedioxythiophene) by hydroxymethyl and oligo(oxyethylene) substituents,” Electrochem. Commun.2(1), 72–76 (2000). [CrossRef]

Electrochim. Acta

• C. Zhang, Y. Xu, N. Wang, Y. Xu, W. Xiang, M. Ouyang, and C. Ma, “Electrosyntheses and characterizations of novel electrochromic copolymers based on pyrene and 3,4-ethylenedioxythiophene,” Electrochim. Acta55(1), 13–19 (2009). [CrossRef]
• P. Camurlu, Z. Bicil, C. Gültekin, and N. Karagoren, “Novel ferrocene derivatized poly(2,5-dithienylpyrrole)s: Optoelectronic properties, electrochemical copolymerization,” Electrochim. Acta63, 245–250 (2012). [CrossRef]
• C. Ma, M. Taya, and C. Xu, “Flexible electrochromic device based on poly(3,4-(2,2 dimethylpropylenedioxy)thiophene),” Electrochim. Acta54(2), 598–605 (2008). [CrossRef]

J. Am. Chem. Soc.

• A. Patra, Y. H. Wijsboom, S. S. Zade, M. Li, Y. Sheynin, G. Leitus, and M. Bendikov, “Poly(3,4-ethylenedioxyselenophene),” J. Am. Chem. Soc.130(21), 6734–6736 (2008). [CrossRef] [PubMed]

J. Electroanal. Chem.

• G. E. Gunbas, P. Camurlu, I. M. Akhmedov, C. Tanyeli, A. M. Onal, and L. Toppare, “A fast switching, low band gap, p- and n-dopable, donor–acceptor type polymer,” J. Electroanal. Chem.615(1), 75–83 (2008). [CrossRef]
• C. Zhang, C. Hua, G. Wang, O. Mi, and C. Ma, “A novel multichromic copolymer of 1,4-bis(3-hexylthiophen-2-yl)benzene and 3,4-ethylenedioxythiophene prepared via electrocopolymerization,” J. Electroanal. Chem.64, 54–61 (2010).

J. Polymer. Sci. Pol. Chem.

• A. C. Kucuk, F. Yilmaz, H. Can, H. Durmaz, A. Kosemen, and A. E. Muftuoglu, “Synthesis of a novel macroinimer based on thiophene and poly(e-caprolactone) and its use in electrochromic device application,” J. Polymer. Sci. Pol. Chem.49, 4180–4192 (2011).

Macromol. Chem. Phys.

• D. Baran, G. Oktem, S. Celebi, and L. Toppare, “Neutral-state green conjugated polymers from pyrrole bis-substituted benzothiadiazole and benzoselenadiazole for electrochromic devices,” Macromol. Chem. Phys.212(8), 799–805 (2011). [CrossRef]

Macromolecules

• B. Sankaran and J. R. Reynolds, “High-contrast electrochromic polymers from alkyl-derivatized poly(3,4-ethylenedioxythiophenes),” Macromolecules30(9), 2582–2588 (1997). [CrossRef]

Mater. Chem. Phys.

• P. R. Somani and S. Radhakrishnan, “Electrochromic materials and devices: present and future,” Mater. Chem. Phys.77(1), 117–133 (2003). [CrossRef]

Nat. Mater.

• P. M. Beaujuge, S. Ellinger, and J. R. Reynolds, “The donor-acceptor approach allows a black-to-transmissive switching polymeric electrochrome,” Nat. Mater.7(10), 795–799 (2008). [CrossRef] [PubMed]

Org. Electron.

• M. Içli, M. Pamuk, F. Algı, A. M. Önal, and A. Cihaner, “A new soluble neutral state black electrochromic copolymer via a donor–acceptor approach,” Org. Electron.11(7), 1255–1260 (2010). [CrossRef]

Science

• G. Shi, S. Jin, G. Xue, and C. Li, “A conducting polymer film stronger than aluminum,” Science267(5200), 994–996 (1995). [CrossRef] [PubMed]

Sol. Energy Mater. Sol. Cells

• P. Camurlu, S. Tarkuc, E. Sahmetlioglu, I. M. Akhmedov, C. Tanyeli, and L. Toppare, “Multichromic conducting copolymer of 1-benzyl-2,5-di(thiophen-2-yl)- 1H-pyrrole with EDOT,” Sol. Energy Mater. Sol. Cells92(2), 154–159 (2008). [CrossRef]

Synth. Met.

• K. Krishnamoorthy, M. Kanungo, A. Q. Contractor, and A. Kumar, “Electrochromic polymer based on a rigid cyanobiphenyl substituted 3,4-ethylenedioxythiophene,” Synth. Met.124(2-3), 471–475 (2001). [CrossRef]

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