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Synthesis and electrochemical investigation of beta-substituted thiophene-based donor–acceptor copolymers with 3,4-ethylenedioxythiophene (EDOT)

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Abstract

The present work reports the synthesis of four electron-acceptor beta-substituted thiophenes that were studied as monomers for electrochemical polymerization with 3,4-ethylenedioxythiophene (EDOT), an electron-donating monomer, aiming the combination of electron-acceptor and donor monomer thiophene to a simpler and convenient build up of novel donor–acceptor copolymeric materials via electrochemical polymerization. Four novel copolymers poly(EDOT-co-3-thiophene phenylacetate), (PEDOT-co-PPhTAc-2a), poly(EDOT-co-3-thiophene(4-nitrophenyl)acetate) (PEDOT-co-PPhTAc-2b), poly(EDOT-co-3-thiophenephenylcarboxylate) (PEDOT-co-PPhTCb), and poly(EDOT-co-3-(phenoxymethyl)thiophene) (PEDOT-co-PPhOMT) were electrochemically polymerized. The monomers were characterized by spectrometric techniques (FTIR, 1H NMR, and 13C NMR), and the copolymers were identified by electrochemical analyses and FT-IR. Although the corresponding homopolymers could not be obtained, in the presence of EDOT, the copolymers were formed in a quasi-reversible electrochemical kinetics. The infrared spectra of the copolymers as well the electrochemical profile corroborates their obtaining. The mass variation during the electrosynthesis was analyzed using a quartz crystal microbalance. The film’s morphologies were investigated by SEM. Interestingly, the combination of electron-rich monomer thiophene (EDOT) and these electron-deficient carboxy-substituted thiophenes might be a convenient building block couple to increase the performance control of physic-chemical properties of mixed polythiophenes with innovative applications and they also showed a possible applicability as charge storage device.

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Acknowledgments

This work was supported by CNPq (457586/2014-1 and 473891/2012-3), CAPES, and FAPEMIG (CEX PPM 00916/15 TEC - APQ-02715-14, and Rede Mineira de Química-RED 00010/14, RQ-MG 2014-2016). We also would like to thank professor Claudinei R. Calado (CEFET-MG) for the SEM measurements.

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  1. Departamento de Química, ICEx - Universidade Federal de Minas Gerais, Belo Horizonte, Brazil

    Marcus Henrique de Araujo, Tulio Matencio, Claudio Luis Donnici & Hállen Daniel Rezende Calado

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  1. Marcus Henrique de Araujo
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  2. Tulio Matencio
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  3. Claudio Luis Donnici
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Correspondence to Marcus Henrique de Araujo or Hállen Daniel Rezende Calado.

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de Araujo, M.H., Matencio, T., Donnici, C.L. et al. Synthesis and electrochemical investigation of beta-substituted thiophene-based donor–acceptor copolymers with 3,4-ethylenedioxythiophene (EDOT). J Solid State Electrochem 20, 2541–2550 (2016). https://doi.org/10.1007/s10008-016-3297-1

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