Abstract
Novel electropolymerized films that naturally appeared gold-like and possessed lustrous green color tones were prepared by the cyclic potential-sweep electropolymerization of 3-methoxythiophene. The polymerized products were characterized by different instrumentation techniques, which identified them as oligo(3-methoxythiophene) containing perchlorate and dodecyl sulfate anions. The optical and structural analyses demonstrated that the films consisted of edge-on and face-on lamellar structures of the oligomers, and that the edge-on structures contributed to the development of the gold-like luster. The role of the cyclic potential sweep was interpreted as the preferential destruction of the face-on lamellar structures and a contribution to the increasing effects of the edge-on lamellar structures.
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Ogura, K., Zhao, R., Yanai, H., Maeda, K., Tozawa, R., Matsumoto, S. & Akazome, M. Facile formation of stable crystals with gold-like metallic luster from organic molecules: 1-aryl-2-(2-thienyl)-5-[5-(tricyanoethenyl)-2-thienyl]pyrroles. Bull. Chem. Soc. Jpn 75, 2359–2370 (2002).
Zhao, R., Akazome, M., Matsumoto, S. & Ogura, K. Novel organic crystals with red-violet metallic luster: 1-aryl-2-(2-thienyl)-5-[5-(tricyanoethenyl)-2-thienyl]pyrrole derivatives bearing a heteroatom combined methyl substituent. Tetrahedron 2, 10225–10231 (2002).
Zhao, R., Matsumoto, S., M. Akazome, M. & Ogura, K. Supramolecular architecture of metal-lustrous inclusion crystals based on aromatic CH-π interaction: versatile inclusion of 1-(p-ethoxyphenyl)-2-(2-thienyl)-5-[5-(tricyanoethenyl)-2-thienyl]pyrrole host with various electron-rich aromatic guest molecules. Tetrahedron 58, 10233–10241 (2002).
Ogura, K., Zhao, R., Jiang, M., Akazome, M., Matsumoto, S. & Yamaguchi, K. Easy formation of gold-like lustrous crystals with a high melting point from 1-aryl-2,5-bis[5-(tricyanoethenyl)-2-thienyl]pyrroles. Tetrahedron Lett. 44, 3595–3598 (2003).
Ogura, K., Zhao, R., Mizuoka, T., Akazome, M. & Matsumoto, S. Formation of gold-like metal-lustrous inclusion crystals from 1-phenyl-2,5-bis[5-(tricyanoethenyl)-2-thienyl]pyrrole host and an electron-donating aromatic guest. Org. Biomol. Chem. 1, 3845–3850 (2003).
Ogura, K., Ooshima, K., Akazome, M. & Matsumoto, S. Formation of metal-lustrous organic crystals from 2-aryl-1-(4-methoxyphenyl)-5-(5-tricyanoethenyl-2-thienyl)pyrroles. Tetrahedron 62, 2484–2491 (2006).
Matsumoto, A., Kawaharazuka, M., Takahashi, Y., Yoshino, N., Kawai, T. & Kondo, Y. Gold-colored organic crystals formed from an azobenzene derivative. J. Oleo Sci 59, 151–156 (2010).
Kondo, Y., Matsumoto, A., Fukuyasu, K., Nakajima, K. & Takahashi, Y. Gold-colored organic crystals of an azobenzene derivative. Langmuir 30, 4422–4426 (2014).
Kukino, M., Kuwabara, J., Matsuishi, K., Fukuda, T. & Kanbara, T. Synthesis and metal-like luster of novel polyaniline analogs containing azobenzene unit. Chem. Lett. 39, 1248–1250 (2010).
Yamada, H., Kukino, M., Wang, Z.-A., Miyabara, R., Fujimoto, N., Kuwabara, J., Matsuishi, K. & Kanbara, T. Preparation and characterization of green reflective films of polyaniline analogs containing azobenzene units. J. Appl. Polym. Sci. 132, 41275 (2015).
Goto, H. Crystal-liquid crystal ordered double layer electroactive polymer prepared with phase transition sequential polymerization, showing metallic electrochromism-bronze, silver, and gold. J. Polym. Sci. Pol. Chem. 51, 3097–3102 (2013).
Tagawa, R., Masu, H., Itoh, T. & Hoshino, K. Solution-cast self-assembled films of perchlorate doped oligo(3-methoxythiophene) showing a gold-like luster. RSC Adv. 4, 24053–24058 (2014).
Smith, G. B., Gentle, A., Swift, P., Earp, A. & Mronga, N. Coloured paints based on coated flakes of metal as the pigment, for enhanced solar reflectance and cooler interiors: description and theory. Sol. Energy Mater. Sol. Cells 79, 163–177 (2003).
Maile, F. J., Pfaff, G. & Reynders, P. Effect pigments—past, present and future. Prog. Org. Coat. 54, 150–163 (2005).
Fall, M., Aaron, J.-J., Sakmeche, N., Dieng, M. M., Jouini, M., Aeiyach, S., Lacroix, J. C. & Lacaze, P. C. Electrochemical and spectroscopic properties of poly(3-methoxythiophene) electrosynthesized in an aqueous micellar medium. Synth. Met. 93, 175–179 (1998).
Gningue-Sall, D., Fall, M., Dieng, M. M., Aaron, J.-J. & Lacaze, P. C. Electrosynthesis and characterization of poly(3-methoxythiophene).polybithiophene composite films prepared in micellar media on Pt and Fe substrates. Phys. Chem. Chem. Phys. 1, 1731–1734 (1999).
Fall, M., Dieng, M. M., Aaron, J.-J., Aeiyach, S. & Lacaze, P. C. Role of surfactants in the electrosynthesis and the electrochemical and spectroscopic characteristics of poly(3-methoxythiophene) films in aqueous micellar media. Synth. Met. 118, 149–155 (2001).
Fall, M., Diagne, A. A., Dieng, M. M., Deflorian, F., Rossi, S., Bonora, P. L., Della Volpe, C. & Aaron, J.-J. Electrochemical impedance spectroscopy of poly(3-methoxythiophene) thin films in aqueous LiClO4 solutions. Synth. Met. 155, 569–575 (2005).
Supplementary information in Kim, Y.-W., Tokuda, T., Yagishita, F., Masu, H., Kubo, M., Murashiro, K. & Hoshino, K. Preparation of transparent conducting films with fillers of mixed-valence bicarbazyl nano/microtubes and wires. Chem. Lett. 43, 89–91 (2014).
Chang, A.-C., Blankespoor, R. L. & Miller, L. L. Characterization and spectroelectrochemical studies of soluble polymerized 3-metoxythiphene. J. Electroanal. Chem. 236, 239–252 (1987).
Dong, B., Xu, J., Zheng, L. & Hou, J. Electrodeposition of conductive poly(3-methoxythiophene) in ionic liquid microemulsions. J. Electroanal. Chem. 628, 60–66 (2009).
Sato, M. & Morii, H. Nuclear magnetic resonance studies on electrochemically prepared poly(3-dodecylthiophene). Macromolecules 25, 4364–4372 (1992).
Botta, C. & Stein, P. C. Spectroscopic analysis of structural defects in poly(3-decylthiophene)s: Influence of the polymerization method. J. Phys. Chem. 99, 3331–3337 (1995).
Zakaria, M. R., Abd-Aziz, S., Ariffin, H., Rahman, N. A. A., Yee, P. L. & Hassan, M. A. Comamonas sp. EB172 isolated from digester treatingpalm oil mill effluent as potential polyhydroxyalkanoate (PHA) producer. Afr. J. Biotechnol. 7, 4118–4121 (2008).
Kerwin, S. M. Computer software reviews. J. Am. Chem. Soc. 132, 2466–2467 (2010).
Gottlieb, H. E., Kotlyar, V. & Nudelman, A. NMR chemical shifts of common laboratory solvents as trace impurities. J. Org. Chem. 62, 7512–7515 (1997).
Yamaji, T., Saito, T., Hayamizu, K., Yanagisawa, M. & Yamamoto, O. Spectral Database for Organic Compounds, National Institute of Advanced Industrial Science and Technology (AIST), Japan. Available from: http://sdbs.db.aist.go.jp/sdbs/cgi-bin/direct_frame_top.cgi. Accessed on August 2016
Tanaka, S., Sato, M. & Kaeriyama, K. Electrochemical polymerization of thiophenes containing a methoxy group. Polym. Commun. 26, 303–306 (1985).
Tanaka, S., Sato, M. & Kaeriyama, K. Electrochemical preparation and properties of poly(3-methoxy-2,5-thiophenediyl) and poly(3-methylthio-2,5-thiophenediyl). Synth. Met. 25, 277–288 (1988).
Cattarin, S., Mengoli, G., Musiani, M. M. & Schreck, B. Synthesis and properties of film electrodes from N-substituted carbazoles in acid medium. J. Electroanal. Chem. 246, 87–100 (1988).
Barr, G. E., Sayre, C. N., Connor, D. M. & Collard, D. M. Polymerization of hydrophobic 3-alkylpyrroles from aqueous solutions of sodium dodecyl sulfate. Langmuir 12, 1395–1398 (1996).
Fall, M., Assogba, L., Aaron, J.-J. & Dieng, M. M. Revisiting the electropolymerization of 3,4-dimethoxythiophene in organic and micellar media. Synth. Met. 123, 365–372 (2001).
Farag, A. A. M. & Fadel, M. Optical absorption and dispersion analysis of nanocrystalline perylene-3,4,9,10-tetracarboxylic-3,4,9,10-dianhydride film prepared by dipcoating and its optoelectronic application. Opt. Laser Technol. 45, 356–363 (2013).
El-Nahhas, M. M., Abdel-Khalek, H. & Salem, E. Structural and optical properties of nanocrystalline 3,4,9,10-perylene-tetracarboxylic-diimide thin film. Adv. Condens. Matter Phys 2012, 698934 (2012).
Merano, M., Aiello, A., ’t Hooft, G. W., van Exter, M. P., Eliel, E. R. & Woerdman, J. P. Observation of Goos-Hänchen shifts in metallic reflection. Opt. Express 14, 15928–15934 (2007).
Winokur, M. J., Wamsley, P., Moulton, J., Smith, P. & Heeger, A. J. Structural evolution in iodine-doped poly(3-alkylthiophenes). Macromolecules 24, 3812–3815 (1991).
Prosa, T. J., Winokur, M. J., Moulton, J., Smith, P. & Heeger, A. J. X-ray structural studies of poly(3-alkylthiophenes): An example of an inverse comb. Macromolecules 25, 4364–4372 (1992).
McCullough, R. D., Tristram-Nagle, S., Williams, S. P., Lowe, R. D. & Jayaraman, M. Self-orienting head-to-tail poly(3-alkylthiophenes): new insights on structure-property relationships in conducting polymers. J. Am. Chem. Soc. 115, 4910–4911 (1993).
Aasmundtveit, K. E., Samuelsen, E. J., Guldstein, M., Steinsland, C., Flornes, O., Fagermo, C., Seeberg, T. M., Pettersson, L. A. A., Inganäs, O., Feidenhans’l, R. & Ferrer, S. Structural anisotropy of poly(alkylthiophene) films. Macromolecules 33, 3120–3127 (2000).
Visy, C., Bencsik, G., Németh, Z. & Vértes, A. Synthesis and characterization of chemically and electrochemically prepared conducting polymer/iron oxalate composites. Electrochim. Acta 53, 3942–3947 (2008).
Jose Abad, J., Pérez-GarcÃa, B., Urbina, A., Colchero, J. & Palacios-Lidón, E. Layered self-organized structures on poly(3-octylthiophene) thin films studied by scanning probe microscopy. Eur. Poly. J. 44, 2506–2515 (2008).
Abad, J., Espinosa, N., Ferrer, P., GarcÃa-Valverde, R., Miguel, C., Padilla, J., Alcolea, A., Castro, G. R., Colchero, J. & Urbina, A. Molecular structure of poly(3-alkylthiophenes) investigated by calorimetry and grazing incidence X-ray scattering. Sol. Energy Mater. Sol. Cells 97, 109–118 (2012).
Qu, Y., Li, L., Lu, G., Zhou, X., Su, Q., Xu, W., Li, S., Jidong Zhang, J. & Yang, X. A novel melting behavior of poly(3-alkylthiophene) cocrystals: premelting and recrystallization of component polymers. Polym. Chem. 3, 3301–3307 (2012).
Nagao, Y., Hirata, T., Goto, S., Sano, S., Kakehi, A., Iizuka, K. & Shiro, M. Intramolecular nonbonded S•••O interaction recognized in (acylimino)thiadiazoline derivatives as angiotensin II receptor antagonists and related compounds. J. Am. Chem. Soc. 120, 3104–3110 (1998).
Watanabe, A., Murakami, S., Mori, K. & Kashiwabara, Y. Electronic properties of polypyrrole/n-Si heterojunctions and polypyrrole/metal contacts. Macromolecules 22, 4231–4235 (1989).
Hasegawa, S. & Grey, F. Electronic transport at semiconductor surfaces—from point-contact transistor to micro-four-point probes. Surf. Sci. 500, 84–104 (2002).
Hulvat, J. F. & Stupp, S. I. Anisotropic properties of conducting polymers prepared by liquid crystal templating. Adv. Mater. 16, 589–592 (2004).
Bao, Z., Dodabalapur, A. & Lovinger, A. J. Soluble and processable regioregular poly(3-hexylthiophene) for thin film field-effect transistor applications with high mobility. Appl. Phys. Lett. 69, 4108–4110 (1996).
Sirringhaus, H., Brown, P. J., Friend, R. H., Nielsen, M. M., Bechgaard, K., Langeveld-Voss, B. M. W., Spiering, A. J. H., Janssen, R. A. J., Meijer, E. W., Herwig, P. & de Leeuw, D. M. Two-dimensional charge transport in self-organized, high-mobility conjugated polymers. Nature 401, 685–688 (1999).
Liu, C., Oshima, K., Shimomura, M. & Miyauchi, S. Anisotropic conductivity-temperature characteristic of solution-cast poly(3-hexylthiophene) films. Synth. Met. 156, 1362–1367 (2006).
John, R. & Wallace, G. G. The use of microelectrodes to probe the electropolymerization mechanism of heterocyclic conducting polymers. J. Electroanal. Chem. 306, 157–167 (1991).
Liu, H., Ye, H. & Zhang, Y. Preparation and characterization of PMMA/flaky aluminium composite particle in the presence of MPS. Colloids Surf. A: Physicochem. Eng. Aspects 315, 1–6 (2008).
Acknowledgements
This work was financially supported by the Ogasawara Foundation for the Promotion of Science & Engineering. We would like to thank the Center for Analytical Instrumentation of Chiba University and Prof Shigeru Takahara for the measurements of reflection spectra and GPC analyses.
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Tokuda, T., Hoshino, K. Electropolymerized films of 3-methoxythiophene with a potential sweep-induced gold-like luster. Polym J 48, 1141–1149 (2016). https://doi.org/10.1038/pj.2016.86
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DOI: https://doi.org/10.1038/pj.2016.86
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