Abstract
The preparation of copolymers bearing N-methylcarbazole and 2,7-linked 3,4-ethylenedioxythiophene units has been carried out using the N-methyl-2,7-di(2-(3,4-ethylenedioxythienyl))carbazole monomer, which has been chemically synthesized through the Stille coupling reaction of 2,7-dibromo-N-methylcarbazole and tributyl-stannylated 3,4-ethylenedioxythiophene. Then, the monomer was electropolymerized by chronoamperometry in acetonitrile with 0.1 M LiClO4 under a constant potential of 0.70 V and using steel AISI 316 electrodes. The electrochemical activity and stability, charge–discharge capacity, charge transfer resistance and surface properties (i.e. morphology, topography and wettability) of the resulting polymer have been characterized and compared with those reported for poly(3,4-ethylenedioxythiophene). Finally, the polymer has been obtained by potentiodynamic sweep, applying around 100 cyclic voltammetry steps to an acetonitrile solution of the N-methyl-2,7-di(2-(3,4-ethylenedioxythienyl))carbazole monomer with 0.1 M LiClO4. Results show that although this technique has been mostly used to electropolymerize diheteroaromatic-subtituted carbazoles, the resulting material presents serious disadvantages with respect to that produced by chronoamperometry under a constant potential.
Graphical abstract
Similar content being viewed by others
References
Skotheim TA, Reynolds JR (2007) Handbook of conducting polymers, 3rd edn. CRC Press, Boca Raton
Inzelt G (2008) Conducting polymers—a new era of electrochemistry. Springer, Heidelberg
Heinze J, Frontana-Uribe BA, Ludwigs S (2010) Electrochemistry of conducting polymers—persistent models and new concepts. Chem Rev 110:4724–4771. https://doi.org/10.1021/cr900226k
Fuchigami T, Atobe M, Inagi S (2014) Fundamentals and applications of organic electrochemistry: synthesis, materials, devices. Wiley, Hoboken
Groenendaal L, Zotti G, Aubert P-H, Waybright SM, Reynolds JR (2003) Electrochemistry of poly(3,4-alkylenedioxythiophene) derivatives. Adv Mat 15:855–879. https://doi.org/10.1002/adma.200300376
Groenendaal L, Jonas F, Freitag D, Pielartzik H, Reynolds JR (2000) Poly(3,4-ethylenedioxythiophene) and Its derivatives: past, present, and future. Adv Mat 12:481–494. https://doi.org/10.1002/(SICI)1521-4095(200004)12:7%3c481:AID-ADMA481%3e3.0.CO;2-C
Kirchmeyer S, Reuter K (2005) Scientific importance, properties and growing applications of poly(3,4-ethylenedioxythiophene). J Mater Chem 15:2077–2088. https://doi.org/10.1039/B417803N
Alemán C, Casanovas J (2004) Theoretical investigation of the 3,4-ethylenedioxythiophene dimer and unsubstituted heterocyclic derivatives. J Phys Chem A 108:1440–1447. https://doi.org/10.1021/jp0369600
Hui Y, Bian C, Xia SH, Tong JH, Wang JF (2018) Synthesis and electrochemical sensing application of poly(3,4-ethylenedioxythiophene)-based materials: a review. Anal Chim Acta 1022:1–19. https://doi.org/10.1016/j.aca.2018.02.080
Poater J, Casanovas J, Sola M, Alemán C (2010) Examining the planarity of poly(3,4-ethylenedioxythiophene): consideration of self-rigidification, electronic, and geometric effects. J Phys Chem A 114:1023–1028. https://doi.org/10.1021/jp908764s
Wei Q, Mukaida M, Kirihara K, Naitoh Y, Ishida T (2015) Recent progress on PEDOT-based thermoelectric materials. Materials 8:732–750. https://doi.org/10.3390/ma8020732
Anno H, Nishinaka T, Hokazono M, Oshima N, Toshima N (2015) Thermoelectric power-generation characteristics of PEDOT:PSS thin-film devices with different thicknesses on polyimide substrates. J Electron Mater 44:2105–2112. https://doi.org/10.1007/s11664-015-3668-x
Eom SH, Senthilarasu S, Uthirakumar P, Yoon SC, Lim J, Lee C, Lim HS, Lee J, Lee SH (2009) Polymer solar cells based on inkjet-printed PEDOT: PSS layer. Org Electron 10:536–542. https://doi.org/10.1016/j.orgel.2009.01.015
Aradilla D, Azambuja D, Estrany F, Casas MT, Ferreira CA, Alemán C (2012) Hybrid polythiophene–clay exfoliated nanocomposites for ultracapacitor devices. J Mater Chem 22:13110–13122. https://doi.org/10.1039/C2JM31372C
Aradilla D, Estrany F, Armelin E, Alemán C (2012) Ultraporous poly(3,4-ethylenedioxythiophene) for nanometric electrochemical supercapacitor. Thin Solid Films 520:4402–4409. https://doi.org/10.1016/j.tsf.2012.02.058
Pérez-Madrigal MM, Estrany F, Armelin E, Díaz DD, Alemán C (2016) Towards sustainable solid-state supercapacitors: electroactive conducting polymers combined with biohydrogels. J Mater Chem A 4:1792–1805. https://doi.org/10.1039/C5TA08680A
Allard S, Forster M, Souharce B, Thiem H, Scherf U (2008) Organic semiconductors for solution-processable field-effect transistors (OFETs). Angew Chem Int Ed 47:4070–4098. https://doi.org/10.1002/anie.200701920
Sakamoto S, Okumura M, Zhao Z, Furukawa Y (2005) Raman spectral changes of PEDOT-PSS in polymer light-emitting diodes upon operation. Chem Phys Lett 412:395–398. https://doi.org/10.1016/j.cplett.2005.07.040
Li ZL, Yang SC, Meng HF, Chen YS, Yang YZ, Liu CH, Horng SF, Hsu CS, Chen LC, Hu JP, Lee RH (2004) Patterning-free integration of polymer light-emitting diode and polymer transistor. Appl Phys Lett 84:3558. https://doi.org/10.1063/1.1728301
Fabregat G, Armelin E, Alemán C (2014) Selective detection of dopamine combining multilayers of conducting polymers with gold nanoparticles. J. Phys Chem B 118:4669–4682. https://doi.org/10.1021/jp412613g
Fabregat G, Casanovas J, Redondo E, Armelin E, Alemán C (2014) A rational design for the selective detection of dopamine using conducting polymers. Phys Chem Chem Phys 16:7850–7861. https://doi.org/10.1039/C4CP00234B
Horii T, Shinnai T, Tsuchiya K, Mori T, Kijima M (2012) Synthesis and properties of conjugated copolycondensates consisting of carbazole-2,7-diyl and fluorene-2,7-diyl. J Polym Sci, Part A: Polym Chem 50:4557–4562. https://doi.org/10.1002/pola.26268
Guzel M, Soganci T, Ayranci R, Ak M (2016) Smart windows application of carbazole and triazine based star shaped architecture. Phys Chem Chem Phys 18:21659–21667. https://doi.org/10.1039/C6CP02611G
Guzel M, Soganci T, Karatas E, Ak M (2018) Donor-acceptor type super-structural triazine cored conducting polymer containing carbazole and quinoline for high-contrast electrochromic device. J Electrochem Soc 165:316–323. https://doi.org/10.1149/2.1201805jes
Reig M, Puigdollers J, Velasco D (2018) Solid-state organization of n-type carbazole-based semiconductors for organic thin-film transistors. Phys Chem Chem Phys 20:1142–1149. https://doi.org/10.1039/C7CP05135B
Ma XC, Niu HJ, Wen HL, Wang SH, Lian YF, Jiang XK, Wang C, Bai XD, Wang W (2015) Synthesis, electrochromic, halochromic and electro-optical properties of polyazomethines with a carbazole core and triarylamine units serving as functional groups. J Mater Chem C 3:3482–3493. https://doi.org/10.1039/C4TC02400A
Liu Y, Chao DM, Yao HY (2014) New triphenylamine-based poly(amine-imide)s with carbazole-substituents for electrochromic applications. Org Electron 15:1422–1431. https://doi.org/10.1016/j.orgel.2014.04.015
O’Brien RN, Santhanam KSV (1993) Electrodeposition of zinc on a carbon cathode followed by laser interferometry: evaluation of the growth of the cathodic boundary layer. J Electroanal Chem 352:167–180. https://doi.org/10.1016/0022-0728(93)80262-G
Dubois JE, Desbene-Monvarney AN, Lacaze PC (1982) Polaromicrotribometric and IR, ESCA, electron-paramagnetic-RES spectroscopic study of colored radical films formed by electrochemical oxidation of carbazoles. 2. N-vinylcarbazole. J Electroanal Chem 132:177–190. https://doi.org/10.1016/0022-0728(82)85016-X
Mengoli G, Musiani MM, Schreck B, Zecchin SJ (1988) Electrochemical synthesis and properties of polycarbazole films in protic acid-media. J Electroanal Chem 246:73–86. https://doi.org/10.1016/0022-0728(88)85052-6
Sadki S, Chevrot C (2003) Electropolymerization of 3,4-ethylenedioxythiophene, N-ethylcarbazole and their mixtures in aqueous micellar solution. Electrochim Acta 48:733–739. https://doi.org/10.1016/S0013-4686(02)00742-9
Li W, Michinobu T (2016) Structural effects of dibromocarbazoles on direct arylation polycondensation with 3,4-ethylenedioxythiophene. Polym Chem 7:3165–3171. https://doi.org/10.1039/C6PY00381H
Wang K, Zhang T, Hu Y, Yang W, Shi Y (2014) Synthesis and characterization of a novel multicolored electrochromic polymer based on a vinylene-linked EDOT-carbazole monomer. Electrochim Acta 130:46–51. https://doi.org/10.1016/j.electacta.2014.02.153
Hu B, Zhang X, Liu J, Chen X, Zhao J, Jin L (2017) Effects of the redox group of carbazole-EDOT derivatives on their electrochemical and spectroelectrochemical properties. Synth Met 228:70–78. https://doi.org/10.1016/j.synthmet.2017.04.011
Gaupp CL, Reynolds JR (2003) Multichromic copolymers based on 3,6-bis(2-(3,4-ethylenedioxythiophene))-N-alkylcarbazole derivatives. Macromolecules 36:6305–6315. https://doi.org/10.1021/ma034493e
Data P, Zassowski P, Lapkowski M, Domagala W, Krompiec S, Flak T, Penkala M, Swist A, Soloducho J, Danikiewicz W (2014) Electrochemical and spectroelectrochemical comparison of alternated monomers and their copolymers based on carbazole and thiophene derivatives. Electrochim Acta 122:118–129. https://doi.org/10.1016/j.electacta.2013.11.167
Hu B, Luo W, Jin L, Liu ZC, Wang MN, Zhou LY, Li CY (2016) Electrochemical and spectroelectrochemical properties of poly(carbazole-EDOT)s derivatives functionalized with benzonitrile and phthalonitrile units. ECS J Solid SC 5:P21–P26. https://doi.org/10.1149/2.0091602jss
Sotzing GA, Reddinger JL, Katritzky AR, Soloducho J, Musgrave R, Reynolds JR, Steel PJ (1997) Multiply colored electrochromic carbazole-based polymers. Chem Mater 9:1578–1587. https://doi.org/10.1021/cm960630t
Kawabata K, Goto H (2010) Electrosynthesis of 2,7-linked polycarbazole derivatives to realize low-bandgap electroactive polymers. Synth Met 160:2290–2298. https://doi.org/10.1016/j.synthmet.2010.08.023
Cansu-Ergun EG, Onal AM (2018) Carbazole based electrochromic polymers bearing ethylenedioxy and propylenedioxy scaffolds. J Electroanal Chem 815:158–165. https://doi.org/10.1016/j.jelechem.2018.03.014
Boudreault P-LT, Beaupré S, Leclerc M (2010) Polycarbazoles for plastic electronics. Polym Chem 1:127–136. https://doi.org/10.1039/B9PY00236G
Aristizabal JA, Soto JP, Ballesteros L, Muñoz E, Ahumada JC (2013) Synthesis, electropolymerization, and photoelectrochemical characterization of 2,7-di(thiophen-2-yl)-N-methylcarbazole. Polym Bull 70:35–46. https://doi.org/10.1007/s00289-012-0817-8
Turbiez M, Frère P, Blanchard P, Roncali J (2000) Mixed π-conjugated oligomers of thiophene and 3,4-ethylenedioxythiophene (EDOT). Tetrahedron Lett 41:5521–5525. https://doi.org/10.1016/S0040-4039(00)00888-1
Aradilla D, Estrany F, Armelin E, Aleman C (2012) Ultraporous poly(3,4-ethylenedioxythiophene) for nanometric electrochemical supercapacitor. Thin Solid Films 520:4402–4409. https://doi.org/10.1016/j.tsf.2012.02.058
Ocampo C, Oliver R, Armelin E, Alemán C, Estrany F (2006) Electrochemical synthesis of poly(3,4-ethylenedioxythiophene) on steel electrodes: properties and characterization. J Polym Res 13:193–200. https://doi.org/10.1007/s10965-005-9025-7
Aradilla D, Pérez-Madrigal MM, Estrany F, Azambuja D, Iribarren JI, Alemán C (2013) Nanometric ultracapacitors fabricated using multilayer of conducting polymers on self-assembled octanethiol monolayers. Org Electron 14:1483–1495. https://doi.org/10.1016/j.orgel.2013.03.010
Aradilla D, Estrany F, Alemán C (2013) Synergy of the I−/I3− redox pair in the capacitive properties of nanometric poly(3,4-ethylenedioxythiophene). Org Electron 14:131–142. https://doi.org/10.1016/j.orgel.2012.10.026
Ma X, Zhu D, Mo D, Hou J, Xu J, Zhou W (2015) The fabrication of multilayers of conducting polymers and its high capacitance performance electrode for supercapacitor. Int J Electrochem Sci 10:7941–7954
Acknowledgements
Authors acknowledge MINECO/FEDER (MAT2015-69367-R), Agència de Gestió d’Ajuts Universitaris i de Recerca (2017SGR359), Pontificia Universidad Católica de Valparaíso (DII Grant No. 37.0/2017), CONICYT-FONDEQUIP program NMR 300 (Grant No. EQM 130154) and ECOS-CONICYT (Grant No. C14E05) for financial support. C.E. is grateful to CONICYT for her predoctoral contract (N° 21140976) and funding for the research stay at UPC from the Pontificia Universidad Católica de Valparaiso (Chile). Support for the research of C.A. was received through the prize “ICREA Academia” for excellence in research funded by the Generalitat de Catalunya.
Author information
Authors and Affiliations
Corresponding authors
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
About this article
Cite this article
Escalona, C., Estrany, F., Ahumada, J.C. et al. 2,7-Linked N-methylcarbazole copolymers by combining the macromonomer approach and the oxidative electrochemical polymerization. Polym. Bull. 77, 1233–1253 (2020). https://doi.org/10.1007/s00289-019-02799-8
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00289-019-02799-8