Cover Image

Mathematical description of «polythiophene paradox» for potentiostatic electropolymerization of electrochemically modified thiophenes

V. V. Tkach, S. C. de Oliveira, R. Ojani, O. V. Elenich, P. I. Yagodynets


The phenomenon of "polythiophene paradox" for insoluble polythiophenes based on electrochemically modified monomers has been described theoretically. The corresponding mathematical model was examined using linear theory of stability and bifurcation analysis. Stability conditions of steady state, monotonic and oscillatory instabilities have also been obtained.


polythiophene; electrochemical modification; positively paradox; electropolymerization; stable steady state

Full Text:



Yamamoto T. Molecular assembly and properties of polythiophenes. NPG Asia Materials. 2010;2(2):54-60. doi:10.1038/asiamat.2010.37

Shirakawa H. The discovery of polyacetylene film: The dawning of an era of conducting polymers (Nobel lecture). Angew Chem, Int Ed. 2001;40(14):2575-80. doi:10.1002/1521-3773(20010716)40:14<2574::AID-ANIE2574>3.0.CO;2-N

MacDiarmid AG. Synthetic metals: A novel role for organic polymers (Nobel lecture). Angew Chem, Int Ed. 2001;40(14):2581-90. doi:10.1002/1521-3773(20010716)40:14<2581::AID-ANIE2581>3.0.CO;2-2

Heeger AJ. Semiconducting and metallic polymers: The fourth generation of polymeric materials (Nobel lecture). Angew Chem, Int Ed. 2001;40(14):2591-611. doi:10.1002/1521-3773(20010716)40:14<2591::AIDANIE2591>3.0.CO;2-0

McCullough RD. The chemistry of conducting polythiophenes. Advanced Materials. 1998;10(2):93-116. doi:10.1002/(SICI)1521-4095(199801)10:2<93::AID-ADMA93>3.0.CO;2-F

Yoshida JI, Kataoka K, Horcajada R, Nagaki A. Modern strategies in electroorganic synthesis. Chem Rev. 2008;108(7):2265-99. doi:10.1021/cr0680843

Groenendaal L, Jonas F, Freitag D, Pielartzik H, Reynolds JR. Poly(3,4-ethylenedioxythiophene) and its derivatives: past, present, and future. Advanced Materials. 2000;12(7):481-94. doi:10.1002/(SICI)1521-4095(200004)12:7<481::AIDADMA481>3.0.CO;2-C

Meijer EJ, Leeuw De DM, Setayesh S, Van Veenendaal E, Huisman BH, Blom PWM, Hummelen JC, Scherf U, Klapwijk TM. Solution-processed ambipolar organic field-effect transistors and inverters. Nature Materials. 2003:2(10):678-82. doi:10.1038/nmat978

Jadhav KG. Synthesis of monomers for new conjugated polymers [master's thesis]. University of Massachusetts; 2012. 93 p.

Sharma LK, Kumar S, Singh S, Singh RKP. Electrochemical synthesis of 5-substituted-2-amino (substituted amino)-1,3,4-oxadiazoles at the platinum electrode. Russ J Electrochem. 2010;46(1):34-40. doi:10.1134/S1023193510010040

Singh S, Kumar S, Sharma LK, Singh RKP. A novel electroorganic synthesis of some 2-amino-5-substituted-1,3,4- oxadiazoles at the platinum electrode. J Indian Chem Soc. 2009;86(7):734-8.

Gütz C, Klöckner B, Waldvogel S. Electrochemical Screening for Electroorganic Synthesis. Organic Process Research and Development. 2016;20(1):26-32. doi:10.1021/acs.oprd.5b00377

Roncali J. Conjugated poly(thiophenes): Synthesis, functionalization, and applications. Chem Rev. 1992;92(4):711-38. doi:10.1021/cr00012a009

Krische B, Zagorska M. The polythiophene paradox. Synth Met 1989;28(1–2):263-8. doi:10.1016/0379-6779(89)90531-6.

Aoki K, Mukoyama I, Chen J. Competition between polymerization and dissolution of poly(3-methylthiophene) films. Russ J Electrochem. 2004;40(3):280-5. doi:10.1023/B:RUEL.0000019665.59805.4c

Mostany J, Scharifker BR. Direct microcalorimetric measurement of doping and overoxidation processes in polypyrrole. Electrochim Acta. 1997;42(2):291-301. doi:10.1016/0013-4686(96)00162-4

Mostany J, Scharifker BR. Impedance spectroscopy of undoped, doped and overoxidized polypyrrole films. Synth Met. 1997;87(3):179-85. doi:10.1016/S0379-6779(97)80105-1

Tkach V, Nechyporuk V, Yagodynets P. Descripción matemática de la síntesis electroquímica de polímeros conductores en la presencia de surfactants. Avances en Química [Internet]. 2013[cited 2016];8(1):9-15. Spanish. Available from:

Tkach VV, NechyporukVV, Yagodynets PI. Georgia Chem J. 2011;11:387.

Tkach VV, Nechyporuk VV, Yagodynets PI. Quím. Bras. 2013;7:67.

Tkach V, de Oliveira SC, Maia G, Guenther Soares B, Ojani R, Yagodynets PI. The mathematical description of the electrosynthesis of composites of oxy-hydroxycompounds of cobalt with overoxidized polypyrrole. Chimica Techno Acta. 2016;3(1):85. doi:10.15826/chimtech.2016.3.1.003

Oliveira SCB, Mendes CHS, Filho FFS, Queiroz NL, Nascimento JAM, Nascimento VB. Electrochemical oxidation mechanism of procarbazine at glassy carbon electrode. J Electroanal Chem. 2015;746:51-6. doi:10.1016/j.jelechem.2015.02.033


Copyright (c) 2016 V. V. Tkach, S. C. de Oliveira, R. Ojani, O. V. Elenich, P. I. Yagodynets

© Chimica Techno Acta, 2014-2018
ISSN 2411-1414 (Online), ISSN 2409-5613 (Print)

ROAD logo WorldCat logo DOAJ logo CAS logo BASE logo eLibrary logo